Gadolinium borosilicate scintillation glass, preparation method thereof, reduction-assisted melting device and application of gadolinium borosilicate scintillation glass

Abstract

The invention discloses gadolinium borosilicate scintillation glass as well as a preparation method, a reduction-assisted melting device and application thereof, the scintillation glass comprises a matrix and luminescent central ions dispersed in the matrix, the matrix comprises the following components in percentage by mass: 3-9% of SiO2, 5-10% of B2O3, 0.5-3% of Al2O3, 75-93% of GdF3, Gd2O3 and La2O3, 1-8% of BaF2 and 0.3-1% of LiF, the content of the luminescent central ions is 1-5%, and the content of the luminescent central ions is 1-5%. The sum of the proportions of all the components except the content of the light-emitting central ions is 100%. According to the gadolinium borosilicate scintillation glass prepared by the invention, the density is between 5.979 and 6.078 g / cm < 3 >, the transmittance at 400 nm is between 83.10 and 84.97 percent, the decay time is between 50.9 and 66.1 ns, the light yield is between 1001 and 1710 Ph / Mev, and the refractive index is between 1.691 and 1.697.

Description

Technical Field

[0001] This invention relates to a gadoborosilicate scintillation glass, its preparation method, and its application, specifically to a gadoborosilicate scintillation glass, its preparation method, reduction-assisted melting apparatus, and its application, belonging to the field of luminescent materials. Background Technology

[0002] Scintillators are energy conversion materials that absorb high-energy radiation (X-rays, gamma rays) and convert it into ultraviolet or visible light. They are widely used in high-energy physics, space exploration, medical imaging, and security inspection. The ultraviolet or visible light emitted after absorbing energy is coupled to photomultiplier tubes, charge-coupled devices, and photodiodes via a coupling agent. The output electrical signal is interpreted, recorded, and processed by end electronic devices, ultimately enabling the detection, identification, and quantitative analysis of ionizing radiation and high-energy particles. The core performance requirements for scintillators include high light yield, high density, fast decay, and low cost.

[0003] With technological advancements, higher demands are being placed on the performance of scintillation materials. Traditional scintillation materials include NaI:Tl, CsI:(Tl,Na), Bi4Ge3O:(BGO), and PbWO4:(PWO), but their high production costs, complex processes, and size limitations make them unsuitable for specific applications. In recent years, the academic community both domestically and internationally has conducted extensive research on novel scintillation materials, with the development of scintillation glasses becoming a hot topic. Scintillation glasses are amorphous materials; unlike crystals where atoms are arranged in a specific pattern, the atoms in glass are arranged randomly. They possess advantages such as low production costs, ease of fabrication into large sizes, high formability under arbitrary conditions, and greater freedom in chemical composition. They hold promise for replacing commercially available scintillation crystals in certain applications.

[0004] High density is an important indicator for scintillation glass. Higher density scintillation glass has a stronger ability to absorb and intercept radiation and particles, which is beneficial for improving the detector's detection efficiency. In practical applications, a density of 6 g / cm³ is preferably desired for scintillation glass. 3 However, the scintillation glasses reported so far are still unable to meet this requirement. Moreover, most high-density glass components contain heavy metal oxides such as PbO, Bi2O3, and Lu2O3. However, glasses containing PbO and Bi2O3 have poor environmental compatibility and do not meet the needs of green material development, thus limiting their application.

[0005] In existing research, high-density scintillation glass often suffers from low light yield, while high-light-yield scintillation glass has insufficient density, and it is difficult to optimize transmittance and refractive index in a coordinated manner. Therefore, the preparation of scintillation glass with high density, high light yield, high transmittance and high refractive index remains a challenge in current research. Summary of the Invention

[0006] In view of this, the main objective of the present invention is to provide a gadoborosilicate scintillation glass, its preparation method, reduction-assisted melting apparatus, and applications. The technical problem to be solved is to add a large amount of GdF3 and Gd2O3 as the main components of SiO2 and B2O3, so that the gadoborosilicate scintillation glass simultaneously has high density, high light yield, high transmittance, and high refractive index, significantly reducing the preparation cost of high-performance scintillation glass, facilitating large-scale production, and thus better meeting the requirements of high-energy ray and high-energy particle detection, as well as high-energy physics experiments and nuclear science experiments.

[0007] The objective of this invention and the technical problem it solves are achieved by the following technical solution. This invention proposes a gadolinium borosilicate scintillation glass, which comprises a matrix and luminescent central ions dispersed in the matrix. The proportions of each component in the matrix, by mass percentage, are: SiO2 3~9%, B2O3 5~10%, Al2O3 0.5~3%, GdF3, Gd2O3 and La2O3 75~93%, BaF2 1~8%, LiF 0.3~1%. The content of the luminescent central ions is 1~5wt%, and the sum of the proportions of all the above components, except for the content of the luminescent central ions, is 100%.

[0008] The objectives of this invention and the technical problems solved can be further achieved by the following technical measures.

[0009] Preferably, in the aforementioned gadolinium borosilicate scintillation glass, the luminescent central ion is Ce. 3+ It is introduced in the form of CeO2.

[0010] Preferably, the aforementioned gadolinium borosilicate scintillation glass has a transition temperature of 550-650°C, a glass softening temperature of 600-700°C, and a coefficient of linear expansion of (90-95)×10⁻⁶. -7 / ℃; density is 5.979-6.078 g / cm³ 3 .

[0011] Preferably, the aforementioned gadoborosilicate scintillation glass has a transmittance of 83.1%-84.97% at 400 nm.

[0012] Preferably, the aforementioned gadoborosilicate scintillation glass has a refractive index of 1.691-1.697 at a wavelength of 594 nm.

[0013] Preferably, the aforementioned gadoborosilicate scintillation glass has a fast decay time of 50.9-66.1 ns and a light yield of 1001-1710 ph / MeV.

[0014] The objectives of this invention and the technical problems it solves can be further achieved by the following technical measures. The present invention provides a method for preparing gadolinium borosilicate scintillation glass, comprising the following steps: S1 uses Si, B, Al, Ba, Gd, La, Ce and Li sources as raw materials, weighs and mixes them evenly according to the formula to obtain raw material powder, and weighs the reducing excipients at the same time. S2 Place the uniformly mixed raw materials from step S1 into an alumina crucible and preheat it; S3 places a small alumina crucible containing the batching material into a large quartz crucible sleeve containing the reducing auxiliary material, and covers the entire large quartz crucible with a quartz crucible cover. The large quartz crucible and the small alumina crucible are then placed in a glass melting furnace for melting. The feeding temperature is 1200-1300℃, and then the temperature is raised to 1300-1400℃ for clarification. After clarification and holding at the temperature, the temperature is lowered to 1200-1300℃, and then homogenization is performed to obtain molten glass. S4 The molten glass obtained in step S3 is preheated to 400-600℃ and cast into shape. It is then subjected to constant temperature annealing and cooled to room temperature to obtain the gadolinium aluminum borosilicate scintillation glass.

[0015] The objectives of this invention and the technical problems solved can be further achieved by the following technical measures.

[0016] Preferably, in the aforementioned method for preparing gadolinium borosilicate scintillation glass, in step S1, the Si source is SiO2, the B source is H3BO3, the Al source is Al2O3, the Ba source is BaF2, the Gd source is GdF3 and Gd2O3, the La source is La2O3, the Ce source is CeO2, and the Li source is LiF; the step of uniform mixing is as follows: placing each raw material in an agate mortar and grinding it clockwise for 20-40 minutes using a matching agate grinding rod; the purity of the raw materials is above 99.9%.

[0017] Preferably, in the aforementioned method for preparing gadolinium borosilicate scintillation glass, the purity of the raw material in step S1 is 99.9% or higher.

[0018] Preferably, in the aforementioned method for preparing gadolinium borosilicate scintillation glass, the reducing auxiliary materials in step S1 include graphite powder and graphite rods.

[0019] Preferably, in the aforementioned method for preparing gadolinium borosilicate scintillation glass, in step S1, the amount of graphite powder used is between 3 and 6 times the total mass of the raw materials.

[0020] Preferably, in the aforementioned method for preparing gadolinium borosilicate scintillation glass, in step S1, the graphite rod has a size of Φ5-10mm and is used in quantities of 10-30 rods.

[0021] Preferably, in the aforementioned method for preparing gadolinium borosilicate scintillation glass, in step S2, the preheating temperature is 300-400℃ and the preheating time is 0.5-1h.

[0022] Preferably, in the aforementioned method for preparing gadolinium borosilicate scintillation glass, in step S3, the clarification and heat preservation time is 0.9-3 hours, and the homogenization time is 20-30 minutes.

[0023] Preferably, in the aforementioned method for preparing gadolinium borosilicate scintillation glass, in step S4, the temperature of the isothermal annealing treatment is 400-600℃, and the isothermal annealing treatment time is 1-4h.

[0024] The objectives of this invention and the technical problems it solves can also be achieved by the following technical measures. This invention proposes a scintillator detector, which includes a scintillator made of the aforementioned gadolinium borosilicate scintillator glass.

[0025] The objectives of this invention and the solutions to its technical problems can also be achieved using the following technical measures. This invention proposes a reduction-assisted melting apparatus, comprising a small alumina crucible containing a batch material, the small alumina crucible being disposed within a large quartz crucible sleeve containing reduction auxiliary materials graphite powder and graphite rods, the large quartz crucible sleeve being covered with a quartz crucible cover plate; the graphite powder being placed at the bottom of the large quartz crucible sleeve; and the graphite rods being inserted into the graphite powder.

[0026] Compared with existing technologies, the gadolinium borosilicate scintillation glass, its preparation method, reduction-assisted melting apparatus, and applications described in this invention have the following beneficial effects: The gadolinium aluminum borosilicate scintillation glass of this invention has a density of 5.979-6.078 g / cm³. 3The transmittance at 400 nm is between 83.10% and 84.97%, the decay time is between 50.9 and 66.1 ns, the light yield is between 1001 and 1710 Ph / Mev, and the refractive index is between 1.691 and 1.697. The gadolinium aluminum borosilicate scintillation glass of this invention has a high refractive index, which can reduce the total internal reflection loss of photons at the glass interface, allowing more photons to be captured by the downstream photodetector, improving the light output efficiency, and thus enhancing the sensitivity of the calorimeter to particle energy measurement, adapting to high-precision detection requirements. The high density of the gadolinium aluminum borosilicate scintillation glass allows for a reduction in the thickness of the glass unit while meeting energy detection requirements, thereby reducing the overall weight of the detector array and adapting to the requirements of lightweight and compact detector structural design. The scintillation glass of this application has high transmittance characteristics, which can effectively reduce the absorption loss of photons during transmission within the glass, ensuring that more photons reach the photodetector from the glass's exit surface, improving the effective acquisition rate of the optical signal, and thus enhancing the accuracy and stability of the detector's particle energy measurement, better adapting to the detector's requirements for high signal-to-noise ratio detection.

[0027] The gadolinium aluminum borosilicate scintillation glass and its preparation method provided by this invention have the characteristics of low cost of raw materials and reducing agents, simple process, short cycle, easy control of composition, easy realization of large-size preparation and excellent chemical stability; moreover, the glass does not contain PbO, has good human and environmental compatibility, and does not contain precious metal oxides such as Lu2O3, which helps to reduce the preparation cost of high-density scintillation glass and facilitates large-scale production, promotion and application. The low-cost, high-performance gadolinium aluminum borosilicate scintillating glass of this invention is rich in GdF3, Gd2O3, and La2O3. Among them, GdF3, as a heavy metal fluoride, has high density characteristics and can also act as a flux to lower the glass melting temperature and increase the solubility of rare earth oxides. The total mass percentage of the three components in this scintillating glass can reach up to 96%, which can significantly increase the glass density to 6 g / cm³. 3 The addition of La2O3 and BaF2 helps to increase the refractive index of the glass, significantly raising it to 1.697; Gd 3+ Capable of reaching Ce 3+ Energy transfer at the luminescent center improves luminescence efficiency, achieving a maximum light yield of 1710 ph / Mev under 137Cs γ-ray excitation, with a transmittance of 84.97% at 400 nm. This invention employs a melt-quenching method and utilizes a self-designed reduction-assisted melting device to prepare gadolinium aluminum borosilicate scintillation glass in a graphite (combination of graphite powder and graphite rod) reducing atmosphere. This glass combines high light yield, fast decay, high density, high transmittance, and high refractive index characteristics, and also has advantages such as low cost, simple process, and easy large-size preparation. This invention uses a combination of industrial-grade graphite rods and graphite powder as a solid-state reducing medium, significantly reducing costs, and the solid-state properties avoid the risk of hazardous gas leakage. Unlike traditional processes that involve adding a built-in reducing agent, this invention utilizes an external graphite reducing atmosphere technology to precisely solve problems such as glass graying caused by difficulty in controlling the amount of a built-in reducing agent, component segregation due to excessive Si source, and difficulties in glass formation. This results in the high-quality preparation of scintillation glass using a low-cost, highly stable solid-state reduction system, improving process stability and overall stability. Attached Figure Description

[0028] Figure 1 These are schematic diagrams of graphite reducing agent-assisted melting in Examples 1-8 and Comparative Examples 1-5 of the present invention; where a and b are the internal structures of the reducing agent-assisted melting device, and c is the overall external structure of the reducing agent-assisted melting device. Reference numerals are as follows: 1-Large crucible sleeve; 2-Large crucible cover plate; 3-Glass feeder; 4-Small crucible (containing glass feeder); 5-Graphite rod; 6-Graphite powder; Figure 2 These are photographs of the processed scintillation glass obtained in Embodiments 1, 5, and 7 of the present invention. Figure 3 The transmittance spectra of the scintillation glass obtained in Examples 1, 5, and 7 of the present invention are shown. Figure 4 The refractive index spectra of the scintillation glass obtained in Examples 1, 5, and 7 of the present invention are shown. Figure 5 The light yield diagrams of the scintillation glass obtained in Embodiments 1, 5, and 7 of the present invention are shown. Detailed Implementation

[0029] To further illustrate the technical means and effects adopted by the present invention to achieve its intended purpose, the following detailed description, in conjunction with preferred embodiments, details the specific implementation methods, structures, features, and effects of the gadolinium borosilicate scintillation glass, its preparation method, reduction-assisted melting apparatus, and its application based on the present invention. 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.

[0030] Unless otherwise specified, all materials and reagents mentioned below are commercially available products well-known to those skilled in the art; unless otherwise specified, all methods described are methods known in the art. Unless otherwise defined, the technical or scientific terms used should have the ordinary meaning understood by those skilled in the art. Where specific experimental steps or conditions are not specified below, they can be performed according to the conventional experimental steps or conditions described in the literature in this field.

[0031] According to some embodiments of the present invention, gadolinium aluminum borosilicate scintillation glass and its preparation method are provided. The scintillation glass comprises a matrix and luminescent center ions dispersed in the matrix. The energy transfer phenomenon between the glass matrices can effectively improve the luminescence efficiency of Ce ions in the scintillation glass. The proportions of each component in the matrix by mass percentage are: SiO2 3~9%, B2O3 5~10%, Al2O3 0.5~3%, GdF3, Gd2O3 and La2O3 75~93%, BaF2 1~8%, LiF 0.3~1%, and the luminescent center Ce... 3+ The content of the component is 1~5wt%, and the sum of the proportions of the above components, except for the content of the luminescent central ion, is 100%. The luminescent central ion is Ce. 3+ Ce 3+ It is introduced in the form of CeO2, which is an external doping agent.

[0032] The functions and contents of each component are selected as follows: Silica (SiO2) acts as a network forger in glass, forming the glass network framework. When the SiO2 content is less than 3 wt%, the glass density drops rapidly, failing to meet the high-density requirements of scintillator glass for calorimeters in circular electron-positron colliders. When the SiO2 content is greater than 9 wt%, the interconnectivity of silicon-oxygen tetrahedra decreases, reducing the glass's stability. Therefore, this invention selects a SiO2 content between 3 and 9 wt% in the scintillator glass to achieve a glass density greater than 6 g / cm³. 3 .

[0033] Boron trioxide (B2O3) is an important component of glass. It can improve the stability of glass, increase its refractive index, improve its gloss, and has good fluxing properties, accelerating the refining of glass and reducing its crystallization ability. However, when its content is greater than 10 wt%, it can cause phase separation in the glass; while when it is less than 5 wt%, it results in poor thermal stability of the glass.

[0034] Aluminum oxide (Al₂O₃) is an intermediate oxide that reduces the crystallization tendency of glass and improves its chemical stability, thermal stability, mechanical strength, hardness, and refractive index. Excessive Al₂O₃ content easily leads to glass crystallization, reducing light transmittance; insufficient Al₂O₃ content results in inadequate chemical stability and mechanical strength. However, when its content exceeds 3 wt%, it easily leads to glass crystallization and reduced light transmittance; while the absence of Al₂O₃ results in insufficient chemical stability and mechanical strength.

[0035] Barium fluoride (BaF2) is used as a barium source to lower the phonon energy of the glass, reduce the nonradiative relaxation probability, and decrease the radiative length of the glass. BaO is introduced into the glass via BaF2. This BaO is a network-external oxide, and through Ba...2+ Polarized bridging oxygen weakens Si-O / BO bonds, reducing melt viscosity to aid melting, while simultaneously regulating network polymerization degree to improve glass-forming ability. The BaF2 content is set within the range of 1–8 wt%. When the BaF2 content is higher than 8 wt%, insufficient fluxing occurs, and the glass is prone to crystallization; while when the BaF2 content is lower than 8 wt%, the mechanical strength of the glass decreases.

[0036] Lithium fluoride (LiF) serves as the lithium source, acting as a high-temperature flux and accelerating glass melting. LiF introduces Li₂O into the glass. This Li₂O is a network-external oxide. LiF provides free oxygen, increasing the O / Si ratio in the glass structure, causing bond breaking, and thus reducing melt viscosity to enhance melting and improve glass-forming ability. The LiF content is set within the range of 0.3% to 1%. When the LiF content is less than 0.3 wt%, insufficient fluxing occurs, and the glass is prone to crystallization; when the LiF content is higher than 1 wt%, the network becomes excessively loose, leading to a decrease in mechanical strength.

[0037] Ce in cerium oxide (CeO2) is the luminescent center element for photoluminescence, and CeO2 serves as both a functional ion source and a structural regulator: Ce 4+ / Ce 3+ Ion pairs can act as scintillation centers, absorbing radiation and then emitting fluorescence through 4f-5d energy level transitions. They are the core active components for glass scintillation performance, and their content is set in the range of 1-5 wt%. When the CeO2 content is below 1 wt%, insufficient light yield will result, while when the CeO2 content is above 5 wt%, self-quenching may occur, affecting the luminescence performance.

[0038] GdF3, Gd2O3, and La2O3 have relatively large atomic masses, and Gd 3+ With a moderate radius, it can effectively form ion solid solutions with most glass matrices, Gd 3+ Energy can be transferred to the luminous center Ce. 3+ This can increase light yield. Lanthanum in glass is primarily composed of La. 3+ The state exists, La 3+ With a large radius and high coordination number, it cannot enter the network unless it is a glass-forming organism, and instead resides in the network gaps. This is due to the La... 3+Located in the gaps of the structural network and possessing a high coordination number, La₂O₃-containing glasses have a relatively compact structure and a high refractive index. This invention utilizes high levels of co-doped GdF₃, Gd₂O₃, and La₂O₃ to significantly increase both the glass density and luminous efficiency of the resulting sample, better meeting the requirements of high-energy ray and high-energy particle detection, as well as high-energy physics and nuclear science experiments. Gd₂O₃ and La₂O₃ are network exosomes, belonging to heavy metal oxides, with a combined content ranging from 75% to 93 wt%. Gd₂O₃ is introduced in the form of Gd₂O₃ and GdF₃. Both Gd₂O₃ and La₂O₃ oxides correspond to metal elements with high atomic numbers and densities, both contributing to increasing the density of the scintillator glass. The content of Gd2O3, La2O3 and GdF3 is between 75 and 93 wt%. When the sum of their contents is below 75 wt%, the density of the glass is relatively low. When the sum of their contents is above 93 wt%, the glass is prone to phase separation and has poor glass-forming properties.

[0039] The density of the gadolinium aluminum borosilicate scintillation glass was tested to be between 5.979 and 6.078 g / cm³. 3 Between these values, the transmittance at 400nm is between 83.10% and 84.97%, the light yield is between 1001 and 1710 Ph / Mev, and the refractive index is between 1.691 and 1.697.

[0040] According to some embodiments of the present invention, a method for preparing the above-mentioned gadolinium aluminum borosilicate scintillation glass is also provided, comprising the following steps: S1 weighs out each raw material according to the formula, mixes them evenly, and obtains a compound material; including: using Si source, B source, Al source, Ba source, Gd source, Ce source, and Li source as raw materials, mixing them evenly according to the mass components of the scintillation glass to obtain raw material powder, and simultaneously weighing out the reduction auxiliary materials graphite powder and graphite rod to jointly promote the reduction of the scintillation glass and optimize the luminescence performance. The Si source is SiO2, the B source is H3BO3, the Al source is Al2O3, the Ba source is BaF2, the Gd source is GdF3 and Gd2O3, the La source is La2O3, and the Ce source is Li. 3+The source is CeO2, and the Li source is LiF. The purity of the raw materials is above 99.9%. The graphite powder used as a reducing agent is 600-1000 mesh with a purity of 99.99%. Graphite powder with a mesh size greater than 1000 mesh is prone to flying and mixing into the glass raw materials in the crucible, causing glass contamination. Graphite powder with a mesh size below 600 mesh is prone to agglomeration, leading to uneven reduction and the appearance of bubbles or impurities in the glass. The graphite rod used as a reducing agent is Φ5mm-Φ10mm with a purity of above 99.9%. The amount of graphite powder used is between 3 and 6 times the total mass of the raw glass materials. If the diameter of the graphite rod is greater than Φ10mm, the reduction reaction rate is slow, and the reduction of Ce4+ in the glass is insufficient; if the diameter of the graphite rod is less than Φ5mm, it is prone to melting and causes an unstable reducing atmosphere. When the total amount of graphite powder is greater than 6 times the total mass of the raw glass materials, the graphite powder easily causes glass contamination during glass melting. If the amount of graphite powder is less than three times the total mass of the raw glass ingredients, it can easily lead to insufficient glass reduction, resulting in yellowing. The amount of graphite rods used is 10-30 rods (10g / rod, 100-300g), which is 1-3 times the total mass of the raw glass ingredients. When the total amount of graphite powder in the rods is greater than three times the total mass of the raw glass ingredients, the graphite rods are prone to tipping over during glass melting, contaminating the glass. Graphite powder easily causes glass contamination. If the amount of graphite rods is less than one times the total mass of the raw glass ingredients, it can easily lead to insufficient glass reduction, resulting in yellowing.

[0041] S2: The uniformly mixed raw material powder (excluding reducing additives) from step S1 is placed in an alumina crucible and preheated. The purpose of preheating is to prevent the crucible from cracking due to rapid heating. The uniformly mixed raw material is preheated in an annealing furnace at a temperature of 300-400℃ for 0.5-1 hour. Preheating temperatures below 300℃ can easily cause crucible cracking or uneven melting of the glass material. Preheating temperatures above 400℃ will increase energy consumption or cause premature volatilization or deterioration of the glass material. Preheating times less than 0.5 hours can cause the crucible to crack due to a sudden temperature rise exceeding its tolerance, making it difficult for the glass material to reach a uniform melting state. Preheating times longer than 60 minutes also lead to a continuous increase in energy consumption and can easily cause volatilization or deterioration of components within the glass material.

[0042] S3 places a small alumina crucible containing the batch material into a large quartz crucible sleeve containing reducing agents graphite powder and graphite rods. A quartz crucible cover is then placed over the large crucible to create a reducing atmosphere. The large crucible, along with the small crucible, is placed in a glass melting furnace for melting. The feeding temperature is 1200-1300℃. If the feeding temperature is below 1200℃, the glass material is difficult to melt and tends to clump, leading to decreased melting efficiency. If the feeding temperature is above 1300℃, the glass material is prone to volatilization, increasing crucible consumption. Subsequently, the furnace is heated at a rate of 5-10℃ / min to a temperature of 1300-1400℃ for clarification. If the heating rate is below 5℃ / min, the glass melting cycle is long, and streaks are easily formed in the glass, affecting its luminescent properties. If the heating rate is above 10℃ / min, the glass material melts unevenly, easily crystallizes, and reduces optical uniformity. If the clarification temperature is below 1300℃, the glass will not be sufficiently clarified, easily forming striped bubbles inside the glass, leading to a decrease in luminous efficiency. The clarification temperature should also not exceed 1400℃, mainly to avoid damage to the heating elements and refractory materials in the furnace due to overheating. The clarification time is 0.9-3 hours; a clarification time shorter than 0.9 hours results in insufficient clarification, while a time longer than 3 hours will cause complete consumption of the external reducing agent. After clarification, the temperature is lowered to 1200-1300℃ for homogenization for 20-30 minutes to obtain molten glass. A homogenization temperature below 1200℃ results in incomplete homogenization, leading to structural stress; a temperature above 1300℃ will cause excessively high discharge temperature, generating stress. A homogenization time shorter than 20 minutes results in insufficient homogenization, while a time longer than 30 minutes will cause glass defects. The reducing auxiliary material, graphite powder, is 600-1000 mesh with a purity of 99.99%. The reducing auxiliary material, graphite rod, is Φ5-10mm with a purity of 99.99%. The combustion of graphite rods and graphite powder consumes oxygen within the large crucible, creating a reducing atmosphere inside. The clarification and homogenization process is as follows: the double-layered crucible device with an external cover and containing carbon powder is added to the glass melting furnace. As the glass melts, the temperature is raised to 1300-1400℃ for clarification, and the clarification is maintained at this temperature for 0.9-3 hours. After clarification, the temperature is lowered to 1200-1300℃ for homogenization, which takes 20-30 minutes.

[0043] S4. The molten glass is poured into a stainless steel mold preheated to 400-600℃ and subjected to isothermal annealing for 2-4 hours. It is then cooled to room temperature at a cooling rate of 5-8℃ / min to obtain the low-cost, high-performance gadolinium aluminum borosilicate scintillating glass. The mold is made of stainless steel. The isothermal annealing temperature is 400-600℃. Annealing temperatures above 600℃ can cause glass deformation and may lead to crystallization. Annealing temperatures below 400℃ can cause internal stress in the glass to be difficult to eliminate, making it prone to cracking and affecting its mechanical properties. Holding time longer than 4 hours can cause glass deformation and may lead to crystallization. Holding time less than 2 hours can cause internal stress in the glass to be difficult to eliminate, making it prone to cracking and affecting its mechanical properties. Regarding the cooling rate, a cooling rate > 108℃ / min leads to stress concentration in the glass, making it prone to cracking and reducing optical uniformity; a cooling rate < 85℃ / min prolongs the annealing cycle, making it prone to crystallization and reducing luminous efficiency.

[0044] In addition, the inventors have independently designed a reduction-assisted melting device, the structure of which is as follows: Figure 1 a, Figure 1 b、 Figure 1 As shown in Figure c, the reduction-assisted melting device includes a small alumina crucible 4 containing the batch material 3. The small alumina crucible 4 is placed inside a large quartz crucible sleeve 1 containing the reducing auxiliary materials graphite powder 6 and graphite rods 5. A quartz crucible cover plate 2 is provided on top of the large quartz crucible sleeve 1. The graphite powder 6 is placed at the bottom of the large quartz crucible sleeve 1. The graphite rods 5 are inserted into the graphite powder 6. The insertion of the graphite rods 5 can further consume the oxygen near the large crucible cover plate, so that a reducing atmosphere is formed inside the large crucible.

[0045] This invention addresses the challenges of existing scintillating glasses, which struggle to simultaneously achieve high density, high light yield, high transmittance, and high refractive index, and suffer from high manufacturing costs and complex processes. It employs a melt-quenching process using a self-designed, simplified reduction-assisted melting device to prepare high-performance gadolinium aluminum borosilicate scintillating glass in a graphite (combination of graphite powder and graphite rods) reducing atmosphere. Furthermore, this invention features targeted innovations in the raw material system: SiO2 and B2O3 are the main network forming bodies; optimizing the SiO2 / B2O3 mass ratio increases the scintillating glass density; Al2O3 suppresses phase separation; LiF promotes melting and also enhances the glass's luminescence performance; GdF3, Gd2O3, and La2O3 serve as key high-atomic-weight components; Gd... 3+ With a moderate radius, it achieves effective solid solution with most matrix ions and can transfer energy to Ce. 3+ Luminescent centers to increase light yield; La 3+With a large radius and high coordination number, it occupies the gaps in the structure without participating in the network construction. By occupying gaps and having high coordination number, it makes the glass structure dense and increases the refractive index. By selecting graphite powder and graphite rods of suitable size and quality, the reducing atmosphere required for scintillation glass melting is constructed, achieving synergistic optimization of high light output, high density, high transmittance and high refractive index. It also has the advantages of low cost, simple process and easy large-scale preparation.

[0046] 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.

[0047] The preparation method of the low-cost, high-performance gadolinium aluminum borosilicate scintillation glass provided by the present invention is further illustrated below with specific embodiments. Table 1 below lists the mass percentage composition of the gadolinium borosilicate scintillation glass of the present invention in 8 embodiments and 5 comparative examples.

[0048] The preparation methods of Examples 1-8 and Comparative Examples 1-5 are as follows: The raw materials SiO2, B2O3, Al2O3, LiF, GdF3, Gd2O3, La2O3, and CeO2 were mixed uniformly according to the mass percentages of the components in Examples 1-8 and Comparative Examples 1-5 of Table 1 to obtain mixed raw material powders. The SiO2 raw material was quartz sand, the B2O3 raw material was H3BO3, and the other scintillation glass components were introduced with their corresponding raw materials. The purity of all the above raw materials was 99.99%.

[0049] Weigh out the reducing agent graphite powder (800~1500 mesh), the amount of which is 4 times the total mass of the raw materials, with a purity of 99.99%; weigh out the reducing agent graphite rods, the size of which is Φ8mm, the purity of which is 99.99%, and the amount of which is 20 rods (200g).

[0050] Table 1. Composition (wt%) of Gadolinium Aluminum Borosilicate Scintillation Glass in Examples 1-8 and Comparative Examples 1-5 The obtained mixed raw material powders were ground and mixed evenly in an agate mortar to obtain a batching material, which was poured into an alumina crucible. The quartz alumina crucible containing the batching material was placed in a quartz crucible sleeve containing graphite powder and graphite rods, and a quartz crucible cover was placed on top of the quartz crucible. The quartz crucible and the alumina crucible were then placed in a glass melting furnace for melting. The feeding temperature was 1250℃, followed by a temperature increase to 1350℃ for clarification. After clarification, the temperature was lowered to 1250℃ and then homogenized to obtain a molten glass. The molten glass was quickly poured into a stainless steel mold preheated to 520℃ and subjected to isothermal annealing for 3.5 hours to eliminate internal stress. It was then cooled to room temperature at a cooling rate of 6℃ / min to finally obtain the low-cost, high-performance gadolinium aluminum borosilicate scintillation glass.

[0051] The above-mentioned shimmering glass is processed into the shimmering glass described in this invention after being cut, surface ground and polished.

[0052] The preparation methods for Examples 1 and 2 are as follows: Weigh 150g of raw materials (total weight) according to the mass percentages of the components in Examples 1 and 2 in Table 1, grind and mix them evenly in an agate mortar to obtain a batching material, pour it into a small alumina crucible, and place the small crucible containing the batching material into a large quartz crucible sleeve containing the reducing agent graphite powder (1000 mesh, 600g) and graphite rods. Cover the entire large quartz crucible with a quartz crucible cover. Place the large quartz crucible and the small alumina crucible in a glass melting furnace for melting. The feeding temperature is 1250℃, and the temperature is raised to 1350℃ for clarification under a graphite reducing atmosphere. After clarification, the temperature is lowered to 1250℃, and then homogenized to obtain molten glass. Then, the molten glass is poured into a steel plate mold that has been fully preheated to 520℃. The formed glass is transferred to an annealing furnace for annealing heat treatment at 520℃. After holding at 520℃ for 3.5 hours, it is cooled to room temperature in the furnace to obtain the initial product of scintillation glass. Comparing Example 1 and Example 2, when the SiO2 / B2O3 ratio decreases, the B2O3 content increases, disrupting the compactness of the SiO2 network structure and leading to a decrease in glass packing density. Therefore, the glass density decreases from 5.997 g / cm³ in Example 1. 3 The concentration decreased slightly to 5.986 g / cm³ in Example 2. 3 .

[0053] The preparation method of Example 3 is as follows: Weigh 150g of raw materials (total weight) according to the molar percentages of the components in Example 3 of Table 1. Grind and mix them evenly in an agate mortar to obtain a batching material. Pour the batching material into a small alumina crucible. Place the small alumina crucible containing the batching material into a large quartz crucible containing 600g of graphite powder (1000 mesh) and graphite rods. Cover the entire large crucible with a quartz crucible cover. Place the large crucible and the small crucible together in a glass melting furnace for melting. The feeding temperature is 1250℃. Under a graphite reducing atmosphere, the temperature is raised to 1350℃ for clarification. After clarification, the temperature is lowered to 1250℃, and then homogenized to obtain molten glass. Then, pour the molten glass into a steel plate mold that has been preheated to 520℃. Transfer the formed glass to an annealing furnace for annealing heat treatment. The annealing temperature is 520℃, held for 3.5 hours, and then cooled to room temperature with the furnace to obtain the initial scintillation glass. Comparing Example 1 and Example 2, as the mass ratio of SiO2 / B2O3 continued to decrease, the B2O3 content increased, disrupting the compactness of the SiO2 network structure and leading to a decrease in glass packing density. Therefore, the glass density decreased from 5.986 g / cm³ in Example 2. 3 The concentration decreased slightly to 5.979 g / cm³ in Example 3. 3 .

[0054] The preparation method of Example 4 is as follows: Weigh 150g of raw materials (total weight) according to the molar percentages of the components in Example 4 of Table 1, and grind and mix them evenly in an agate mortar. The resulting batch is poured into a small alumina crucible. This crucible is then placed inside a large quartz crucible containing 600g of graphite powder (1000 mesh) and graphite rods. A quartz crucible cover is then placed over the entire large quartz crucible. The large quartz crucible, along with the small alumina crucible, is placed in a glass melting furnace for melting. The charging temperature is 1250℃, and the temperature is raised to 1300℃ for clarification under a graphite reducing atmosphere. After clarification, the temperature is lowered to 1250℃, followed by homogenization to obtain molten glass. The molten glass is then poured into a steel mold preheated to 520℃. The formed glass is transferred to an annealing furnace for annealing heat treatment at 520℃ for 3.5 hours, followed by furnace cooling to room temperature to obtain a preliminary scintillation glass product. Comparing Example 1 and Example 4, the glass bulk density decreased slightly as the melting temperature decreased, from 5.997 g / cm3 to 5.981 g / cm3.

[0055] The preparation methods for Examples 5 and 6 are as follows: According to the molar percentages of the components in Examples 5 and 6 of Table 1, 150g of raw materials (total weight of raw materials) were weighed and ground evenly in an agate mortar to obtain a compound. This compound was poured into a small alumina crucible, which was then placed inside a large quartz crucible containing 600g of 1000-mesh graphite powder and a graphite rod. A quartz crucible cover was then placed over the entire large crucible. The large and small crucibles were placed in a glass melting furnace for melting. The feeding temperature was 1250℃, and the temperature was raised to 1350℃ for clarification under a graphite reducing atmosphere. After clarification, the temperature was lowered to 1250℃, followed by homogenization to obtain molten glass. The molten glass was then poured into a steel mold preheated to 520℃. The formed glass was transferred to an annealing furnace for annealing heat treatment at 520℃ for 3.5 hours, followed by furnace cooling to room temperature to obtain a preliminary scintillation glass product. Comparing Examples 5 and 6, when the LiF content decreases, the glass phonon energy increases, nonradiative transitions are enhanced, leading to Ce... 3+ The energy loss at the luminescent center increased, and the light yield decreased from 1344 g / cm³ in Example 5. 3 Reduced to 1317 g / cm³ compared to Example 6 3 .

[0056] The preparation methods for Examples 7 and 8 are as follows: According to the molar percentages of the components in Examples 7 and 6 of Table 1, 150g of raw materials (total weight of raw materials) were weighed and ground evenly in an agate mortar to obtain a batching material. This batching material was poured into a small alumina crucible. The small alumina crucible containing the batching material was placed in a large quartz crucible sleeve containing 600g of graphite powder (1000 mesh) and graphite rods as reducing agents. A quartz crucible cover was then placed over the entire large quartz crucible. The large quartz crucible and the small crucible were placed in a glass melting furnace for melting. The feeding temperature was 1250℃, and the temperature was raised to 1350℃ for clarification under a graphite reducing atmosphere. After clarification, the temperature was lowered to 1250℃, and then homogenized to obtain molten glass. The molten glass was then poured into a steel plate mold that had been preheated to 520℃. The formed glass was transferred to an annealing furnace for annealing heat treatment. The annealing temperature was 520℃, and the temperature was held for 3.5 hours. After cooling in the furnace to room temperature, a preliminary scintillation glass product was obtained. Comparing Examples 7 and 8, it is evident that a decrease in Al2O3 leads to easier phase separation in the glass, resulting in Ce... 3 + Uneven distribution reduces energy transfer efficiency, resulting in a decrease in light yield, which drops from 1018 ph / MeV in Example 7 to 1001 ph / MeV in Example 8.

[0057] In comparative examples 1, 5, and 7, the increase in CeO2 led to a decrease in Ce. 3+Increased concentration triggers a concentration quenching effect, leading to increased energy loss between luminescent centers and a decrease in light yield; simultaneously, Ce... 3+ Enhanced cross-relaxation accelerates the energy release rate and shortens the decay time.

[0058] The preparation method of Comparative Example 1 is as follows: Weigh 150g of raw materials (total weight) according to the mass percentage of component 1 in Comparative Example 1 of Table 1. Grind and mix them evenly in an agate mortar to obtain a compound. Pour the compound into a small alumina crucible. Place the small alumina crucible containing the compound into a large quartz crucible containing 600g of graphite powder (600 mesh) and 10 graphite rods. Cover the entire large quartz crucible with a quartz crucible cover. Place the large quartz crucible and the small alumina crucible in a glass melting furnace for melting. The feeding temperature is 1250℃. Under a graphite reducing atmosphere, the temperature is raised to 1350℃ for clarification. After clarification, the temperature is lowered to 1250℃ and then homogenized to obtain molten glass. Then, pour the molten glass into a steel mold that has been preheated to 520℃. The formed glass was transferred to an annealing furnace for annealing heat treatment, held at 520℃ for 3.5 hours, and then cooled to room temperature in the furnace to obtain the initial scintillation glass. Observation showed that the glass was yellow when using 600-mesh graphite powder as a reducing agent, indicating that the graphite powder particle size was too large, resulting in incomplete combustion and failure to form an effective reducing atmosphere inside the large crucible, causing the light yield to drop to 302ph / MeV.

[0059] The preparation method of Comparative Example 2 is as follows: Weigh 150g of raw materials (total weight) according to the mass percentage of components in Comparative Example 2 in Table 1. Grind and mix them evenly in an agate mortar to obtain a batching material. Pour the batching material into a small alumina crucible. Place the alumina crucible containing the batching material into a large quartz crucible sleeve containing 600g of graphite powder (800 mesh) and 10 graphite rods. Cover the entire large crucible with a quartz crucible cover. Place the large quartz crucible and the alumina crucible together in a glass melting furnace for melting. The feeding temperature is 1250℃. Under a graphite reducing atmosphere, the temperature is raised to 1350℃ for clarification. After clarification, the temperature is lowered to 1250℃, and then homogenized to obtain molten glass. Then, pour the molten glass into a steel mold that has been preheated to 520℃. Transfer the formed glass to an annealing furnace for annealing heat treatment. After holding at 520℃ for 3.5h, cool it to room temperature with the furnace to obtain a preliminary scintillation glass product. Observations showed that the glass remained pale yellow when using 800-mesh graphite powder as a reducing agent, which was lighter than that of Comparative Example 1, indicating that the graphite powder particle size was still unsuitable and failed to form an effective reducing atmosphere inside the large crucible. The light yield was 693 ph / MeV, which was significantly lower than the 1018 ph / MeV of Example 7.

[0060] The preparation method of Comparative Example 3 is as follows: Weigh 150g of raw materials (total weight) according to the mass percentages of the three components in the comparative example in Table 1. Grind and mix them evenly in an agate mortar to obtain a compound. Pour the compound into a small alumina crucible. Place the small alumina crucible containing the compound into a large quartz crucible containing 600g of graphite powder (1200 mesh) and 10 graphite rods. Cover the entire large quartz crucible with a quartz crucible cover. Place the large quartz crucible and the small alumina crucible in a glass melting furnace for melting. The feeding temperature is 1250℃. Under a graphite reducing atmosphere, the temperature is raised to 1350℃ for clarification. After clarification, the temperature is lowered to 1250℃, and then homogenized to obtain molten glass. Then, pour the molten glass into a steel mold that has been preheated to 520℃. The formed glass was transferred to an annealing furnace for annealing heat treatment, held at 520℃ for 3.5 hours, and then cooled to room temperature in the furnace to obtain the initial scintillation glass. Observation showed that the glass was colorless and transparent when using 1200-mesh graphite powder as a reducing agent. However, due to the large mesh size and small particle size of the carbon powder, some carbon powder accidentally fell onto the glass surface during discharge, affecting the overall transparency of the glass. The transmittance (400nm) dropped to 76.51%, and the light yield dropped to 993ph / MeV.

[0061] The preparation method of Comparative Example 4 is as follows: Weigh 150g of each of the four raw materials (total weight) according to the mass percentages of the comparative examples in Table 1. Grind and mix them evenly in an agate mortar to obtain a compound. Pour the compound into a small alumina crucible. Place the small alumina crucible containing the compound into a large quartz crucible containing 600g of graphite powder (1000 mesh) and graphite rods. Cover the entire large quartz crucible with a quartz crucible cover. Place the large quartz crucible and the small alumina crucible into a glass melting furnace for melting. The feeding temperature is 1250℃. Under a graphite reducing atmosphere, the temperature is raised to 1350℃ for clarification. After clarification, the temperature is lowered to 1250℃, and then homogenized to obtain molten glass. Then, pour the molten glass into a steel mold that has been preheated to 520℃. The formed glass was transferred to an annealing furnace for annealing heat treatment at 520°C for 3.5 hours, followed by furnace cooling to room temperature to obtain a preliminary glitter glass product. In Example 1 and Comparative Example 4, La 3+ Located in the voids of the structural network and possessing a high coordination number, La₂O₃-containing glasses have a relatively compact structure and a high refractive index. As the lanthanum content in the glass increases, the refractive index (594 nm) decreases from 1.695 in Example 1 to 1.687 in Example 4. Figure 4 As shown.

[0062] The preparation method of Comparative Example 5 is as follows: Weigh 150g of each of the five components in Comparative Example 5 according to the mass percentages in Table 1. Grind and mix them evenly in an agate mortar to obtain a compound. Pour the compound into a small alumina crucible. Place the small alumina crucible containing the compound into a large quartz crucible containing the reducing agent graphite powder (100g) and graphite rods. Cover the entire large quartz crucible with a quartz crucible cover. Place the large quartz crucible and the small alumina crucible in a glass melting furnace for melting. The feeding temperature is 1250℃, and the temperature is raised to 1350℃ under a graphite reducing atmosphere for clarification. The molten glass was clarified and then cooled to 1250°C, followed by homogenization to obtain a molten glass body. The molten glass was then poured onto a steel mold preheated to 520°C. The formed glass was transferred to an annealing furnace for annealing heat treatment at 520°C for 3.5 hours, followed by furnace cooling to room temperature to obtain a preliminary scintillation glass product. When the gadolinium oxide content increased, the glass density increased, because the molar mass of gadolinium oxide was significantly higher than that of the conventional components in the glass network, and its enrichment increased the mass per unit volume, raising the glass density from 5.997 g / cm³ in Example 1. 3 It decreased to 5.859 / cm² in Comparative Example 5. 3 .

[0063] The preparation method of Comparative Example 6 is as follows: Weigh 150g of each of the six components in Comparative Example 1 according to their respective mass percentages. Grind and mix them evenly in an agate mortar to obtain a compound. Pour the compound into a small alumina crucible. Place the small alumina crucible containing the compound into a large quartz crucible containing the reducing agent graphite powder (100g) and graphite rods. Cover the entire large quartz crucible with a quartz crucible cover. Place the large quartz crucible and the small alumina crucible in a glass melting furnace for melting. The feeding temperature is 1250℃. Under a graphite reducing atmosphere, the temperature is raised to 1350℃ for clarification. After clarification, the temperature is lowered to 12℃. The glass was heated to 50℃ and then homogenized to obtain molten glass. The molten glass was then poured onto a steel mold preheated to 520℃. The formed glass was transferred to an annealing furnace for annealing heat treatment at 520℃ for 3.5 hours, followed by furnace cooling to room temperature to obtain a preliminary scintillation glass product. When the lithium fluoride content decreased to 0.1 wt%, while maintaining the same glass melting process, white infusible substances appeared on the surface of the molten glass, leading to a decrease in transmittance (78.27%) and light yield (848 ph / MeV) at 400 nm, demonstrating that lithium fluoride has a melting-promoting effect. Figure 3 and 5 The image shows a comparison between Example 1 and Comparative Example 6.

[0064] The heat-treated glass from Examples 1-8 and Comparative Examples 1-6 was then cut, ground, and polished. It was cut into pieces 40.1 mm long * 40.1 mm wide * 10.1 mm thick using a 0.5 mm thick mechanical blade, and then manually ground with sandpaper for 2 hours. Subsequently, both ends of the glass were polished with a 1.2 M cerium oxide polishing solution (commercially available) until the surface roughness Ra was less than 0.01 mm, resulting in a scintillation glass sample 40 mm long × 40 mm wide × 10 mm thick.

[0065] The corresponding performance of Examples 1-8 and Comparative Examples 1-6 of the present invention is shown in Table 2.

[0066] Table 2 Corresponding properties of the glasses in Examples 1-8 and Comparative Examples 1-6 The densities of the glass samples in the embodiments and comparative examples of this invention were measured using an MH-1200F balance manufactured by Chung Lung Instruments Co., Ltd. The measurement principle is Archimedes' displacement method, and the liquid used in the test was deionized water. The measurement principle is shown in equation (1) below.

[0067] (1) Wherein, ρ is the density of the glass to be tested, Ma is the mass of the glass measured in air, M1 is the mass of the glass measured in liquid, ρ1 represents the density of the "water" displaced during the test (which is deionized water used in this invention), and ρa is the air density at room temperature.

[0068] The embodiments and comparative examples of this invention used a Hitachi U-4100 ultraviolet-visible spectrophotometer from Japan, employing double-sided polished transparent scintillation glass for testing. The entire testing was conducted at room temperature, with a testing range of 200-1100 nm and a resolution of 1 nm. The testing principle is that when light passes through the scintillation glass, the dopant ions in the glass absorb a portion of the photon energy matching the energy difference between its energy levels, thus reducing the transmittance of that wavelength band. Therefore, when a beam of light shines on the glass, reflection and scattering result in some light loss, and absorption by the glass material further reduces light loss. The remaining light passes through the material and is received by the receiver at the other end. As the wavelength of the emitted light source changes, the spectral lines composed of the light source wavelength and the material's transmittance properties constitute the transmission spectrum.

[0069] The decay time was tested using a PMT XP2020; the light yield of all scintillation glasses was measured in γ-ray transmission mode at a 662 KeV 137Cs source. The composition of the scintillation glasses for Examples 1-8 and Comparative Examples 1-6 is shown in Table 1, and the density, refractive index, transmittance, light yield, coefficient of linear expansion, and decay time are shown in Table 2. Figure 2The photographs (40×40×10mm) show the actual scintillation glass obtained in Embodiments 1, 5, and 7 of the present invention after mechanical processing. The top and bottom surfaces, which are 40mm long and 40mm wide, have been polished to facilitate the testing of optical and luminous core performance.

[0070] The glass described in this invention is used in the hadron calorimeter of the Circular Electron-Positron Collider (CEPC). The CEPC calorimeter is a key piece of equipment, containing scintillator units, and has the functions of detecting energy, position, and time. The scintillator glass selected in Example 1 has a density of 5.997 g / cm³. 3 The light emission performance is 1710ph / MeV and the decay time is 62.7ns. As a unit, it is fused and processed into a 50×50×10mm cube and the surface is ground and polished. Several units are arranged in a specific way to form a detection array.

[0071] Numerous specific details are set forth in this specification. However, it will be understood that embodiments of the invention may be practiced without these specific details. In some embodiments, well-known methods, structures, and techniques have not been shown in detail so as not to obscure the understanding of this specification.

[0072] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0073] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

[0074] 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 gadolinium borosilicate scintillating glass characterized in that, The scintillation glass comprises a matrix and luminescent center ions dispersed in the matrix, and the proportions of the components in the matrix are as follows in terms of mass percentage: SiO2 23-9%, B2O3 5-10%, Al2O3 0.5-3%, GdF3, Gd2O3 and La2O3 75-93%, BaF2 1-8%, LiF 0.3-1%, and the content of the luminescent center ions is 1-5 wt%, and the sum of the proportions of the above components except the content of the luminescent center ions is 100%.

2. The gadolinia borosilicate scintillating glass of claim 1, wherein, The luminescence center ions are Ce 3+ which are introduced in the form of CeO2.

3. The gadolinia borosilicate scintillating glass of claim 1, wherein, The transition temperature of the gadolinium borosilicate scintillation glass is 550-650 DEG C, the glass softening temperature is 600-700 DEG C; the linear expansion coefficient is (90-95) x 10 -7 / DEG C; the density is 5.979-6.078 g / cm 3 ; the transmittance at 400 nm is 83.10%-84.97%; the refractive index at wavelength 594 nm is 1.691-1.697; the decay time is 50.9-66.1 ns; and the light yield is 1001-1710 ph / MeV.

4. A method of making a gadolinium borosilicate scintillating glass, characterized in that, The method comprises the following steps: S1, taking Si source, B source, Al source, Ba source, Gd source, La source, Ce source and Li source as raw materials, weighing and mixing according to the formula to obtain raw material powder, and weighing reducing auxiliary materials at the same time; S2, placing the uniformly mixed raw materials of step S1 in an alumina small crucible and preheating; S3, placing the alumina small crucible containing the batch materials in a quartz large crucible set containing the reducing auxiliary materials, covering the upper part of the quartz large crucible with a quartz crucible cover plate, and placing the quartz large crucible together with the alumina small crucible in a glass melting furnace for melting, the feeding temperature is 1200-1300℃, then the temperature is raised to 1300-1400℃ for fining, after fining and holding, the temperature is lowered to 1200-1300℃, then homogenization treatment is carried out, and a molten glass body is obtained; S4, preheating the molten glass body obtained in step S3 to 400-600℃ for casting forming, constant temperature annealing treatment, cooling to room temperature, and obtaining the gadolinium aluminum borosilicate scintillation glass.

5. The method of making gadolinium borosilicate scintillating glass according to claim 4, wherein, In step S1, the Si source is SiO2, the B source is H3BO3, the Al source is Al2O3, the Ba source is BaF2, the Gd source is GdF3 and Gd2O3, the La source is La2O3, the Ce source is CeO2, and the Li source is LiF; the uniformly mixing step is: placing each raw material in an agate mortar, and grinding along the clockwise direction for 20-40 min by using a matched agate grinding rod; the purity of the raw materials is more than 99.9%.

6. The method of making gadolinium borosilicate scintillating glass of claim 4, wherein, In step S1, the reducing auxiliary materials comprise graphite powder and graphite rods.

7. The method of making gadolinium borosilicate scintillating glass according to claim 6, wherein, In step S1, the amount of the graphite powder is 3-6 times the total mass of the raw materials; the size of the graphite rods is Φ5-10 mm, and the amount is 10-30 rods.

8. The method of making gadolinium borosilicate scintillating glass of claim 6, wherein, In step S2, the preheating temperature is 300-400℃, and the preheating time is 0.5-1 h; in step S3, the fining holding time is 0.9-3 h, and the homogenization time is 20-30 min; in step S4, the temperature of the constant temperature annealing treatment is 400-600℃, and the constant temperature annealing treatment time is 1-4 h.

9. A scintillator detector, characterized by It comprises a scintillator composed of the gadolinium borosilicate scintillation glass according to any one of claims 1-3.

10. A reduction assisted melting apparatus characterized by comprising: The reducing auxiliary melting device comprises an alumina small crucible containing batch materials, the alumina small crucible is arranged in a quartz large crucible set containing reducing auxiliary materials graphite powder and graphite rods, a quartz crucible cover plate is arranged on the upper part of the quartz large crucible set; the graphite powder is placed in the bottom layer of the quartz large crucible set; and the graphite rods are inserted in the graphite powder.

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