Boron gadolinium silicate scintillation glass with wide aluminum content range and high light yield as well as preparation method and application of boron gadolinium silicate scintillation glass

Abstract

The invention discloses high-light-yield boron gadolinium silicate scintillation glass with a wide aluminum content range and a preparation method and application of the high-light-yield boron gadolinium silicate scintillation glass. The scintillation glass comprises a matrix and light-emitting central ions dispersed in the matrix, the boron-gadolinium silicate scintillation glass with the wide aluminum content range and the high light yield comprises a matrix and light-emitting central ions dispersed in the matrix, wherein the matrix comprises the following components in percentage by mass: 3-15% of silicon dioxide, 5-15% of silicon dioxide, 5-15% of silicon dioxide, and the balance of water. 4 to 11% of diboron trioxide; 50 to 70% of gadolinium oxide; 6-20% of gadolinium fluoride; 4-20% of aluminum oxide; 1-3% of gallium oxide; 2-5 parts of barium oxide; 0.5 to 1.5 percent of calcium oxide; the content of the luminescent central ions is 2-9%, and the sum of the proportions of the components is 100%. The gadolinium borosilicate scintillation glass is characterized in that gadolinium trioxide, silicon dioxide and diboron trioxide are used as main components, a large amount of aluminum oxide is added, so that the gadolinium borosilicate scintillation glass has high density, high light yield and high transmittance, and the preparation cost of the high-performance scintillation glass is remarkably reduced.

Description

Technical Field

[0001] This invention relates to a high-yield borosilicate scintillation glass with a wide range of aluminum content, its preparation method, and its applications, belonging to the field of luminescent materials. Background Technology

[0002] Scintillation glass is relatively inexpensive to prepare, with abundant raw material reserves, a simple preparation process, and is easily mass-produced industrially. This primarily solves the problem of difficult preparation of crystal scintillator materials. Rare-earth-doped glass scintillators allow for maximal control over the type and proportion of rare-earth ions, thus ensuring the required luminescence performance of the scintillator material. Depending on the application environment, we can dope it with materials such as Ce. 3+ 、Tb 3+ Eu 3+ Ho 3+ Pr 3+ Different rare-earth ion activators essentially cover all luminescence bands in the ultraviolet and visible light spectrum, and each ion has a different luminescence decay time, ranging from nanoseconds to milliseconds. These different decay times can address different fast and slow events. Rare earth Ce 3+ Ions, due to their ability to allow 5d-4f electric dipole transitions and thus exhibit nanosecond-level decay characteristics, have become the preferred activators for both crystalline and amorphous scintillation materials. Traditional glass systems are numerous, including silicates, borosilicates, germanates, and tellurates, but currently, scintillation glasses in use are limited to silicate systems. Borosilicate glasses exhibit good chemical stability, high strength, and good ductility, making them suitable for various working environments.

[0003] In the field of scintillation glass, luminous yield is the core indicator determining its radiation detection sensitivity, and improving this performance is crucial for expanding its applications in nuclear medicine, industrial inspection, and other fields. Gadolinium, due to its excellent X-ray absorption and energy conversion capabilities, has become a key component for optimizing scintillation performance, while the gadolinium source morphology directly affects product performance and cost. Traditionally, when gadolinium oxide is used as the gadolinium source, it tends to agglomerate during glass melting, hindering energy transfer and making it difficult to achieve high luminous yield targets. To overcome this bottleneck, the industry has developed a technical approach of replacing a portion of gadolinium oxide with a high proportion of gadolinium fluoride. Fluoride ions in gadolinium fluoride can reduce the viscosity of the glass melt, promote uniform dispersion of gadolinium ions, reduce quenching of luminescent centers, and simultaneously regulate the glass network structure to reduce non-radiative transitions, resulting in a luminous yield increase of more than 30% compared to the pure gadolinium oxide system. The performance of some products approaches that of single-crystal scintillators, laying the foundation for high-precision detection applications. However, the high price of gadolinium fluoride remains a major pain point for large-scale applications. Its preparation requires multiple complex processes, and its market price is 5-8 times that of gadolinium oxide. Gadolinium fluoride accounts for over 60% of the cost, limiting its application in cost-sensitive fields. Furthermore, gadolinium fluoride production is concentrated, making supply susceptible to raw material fluctuations and environmental policies, resulting in price volatility of 20%-40%. High-proportion use can corrode melting equipment, requiring specialized equipment to further increase costs. Therefore, a low-cost alternative is urgently needed.

[0004] In existing research, scintillation glass often suffers from low light yield, and it is difficult to optimize high density, transmittance and cost in a coordinated manner. Therefore, the preparation of scintillation glass with high light yield, high density, high transmittance and low cost remains a challenge for current research. Summary of the Invention

[0005] In view of this, the main objective of the present invention is to provide a high-yield borobosilicate scintillation glass with a wide range of aluminum content, its preparation method, and its application. The technical problem to be solved is to add a large amount of aluminum oxide to gadolinium oxide, silicon dioxide, and boron oxide as the main components, so that the gadolinium borosilicate scintillation glass simultaneously has high density, high light yield, and high transmittance, significantly reducing the preparation cost of high-performance scintillation glass, facilitating large-scale production, and thus better meeting the application requirements of medical imaging, industrial non-destructive testing, and security inspection.

[0006] The objective of this invention and the technical problem it solves are achieved by the following technical solution. This invention proposes a high-yield borosilicate scintillation glass with a wide aluminum content range. The high-yield borosilicate scintillation glass with a wide aluminum content range comprises a matrix and luminescent central ions dispersed in the matrix. The proportions of each component in the matrix, by mass percentage, are: silicon dioxide 3-15%; boron trioxide 4-11%; gadolinium trioxide 50-70%; gadolinium fluoride 6-20%; aluminum trioxide 4-20%; gallium oxide 1-3%; barium oxide 2-5%; calcium oxide 0.5-1.5%; scandium oxide 0.3-1.2%. The content of the luminescent central ions is 2-9%, and the sum of the proportions of the above components is 100%.

[0007] The objectives of this invention and the technical problems solved can be further achieved by the following technical measures.

[0008] Preferably, the aforementioned high-yield borosilicate scintillation glass with a wide aluminum content range, wherein the luminescent central ion is Ce. 3+ .

[0009] Preferably, the aforementioned high-yield borosilicate scintillation glass with a wide aluminum content range has a density between 5.8769 and 6.0047 g / cm³.

[0010] Preferably, the aforementioned high-yield borosilicate scintillation glass with a wide range of aluminum content has a transmittance of 83.27-86.76% at 400 nm.

[0011] Preferably, the aforementioned high-yield borosilicate scintillation glass with a wide aluminum content range has a decay time between 54.2 and 68.3 ns.

[0012] Preferably, the aforementioned high-yield borosilicate scintillation glass with a wide aluminum content range has a light yield between 1184 and 1694 Ph / Mev.

[0013] Preferably, the aforementioned high-yield borosilicate scintillation glass with a wide aluminum content range has a refractive index between 1.6920 and 1.6985 Ph / Mev.

[0014] The objective of this invention and the technical problem it solves can be further achieved by the following technical measures. The present invention proposes a method for preparing a high-yield borosilicate scintillation glass with a wide aluminum content range, comprising the following steps: S1 uses Si, B, Gd, Al, Ga, Ba, Ca, Ce and Sc sources as raw materials. The raw materials are weighed and mixed evenly according to the formula to obtain raw material powder, which is dried at 90-100℃ for 1-2 hours. At the same time, the reducing auxiliary materials are weighed. S2 Place the uniformly mixed raw materials from step S1 into a small crucible with a cover plate; open the inlet and outlet valves of the vacuum furnace and introduce 500-600 sccm of high-purity argon gas for 10 minutes. S3. Place the small crucible containing the batch material into the large crucible sleeve containing the reducing auxiliary material, and place the large crucible together with the small crucible into a glass melting vacuum furnace at room temperature for melting, and turn on the circulating cooling water; after sealing the furnace body, adjust the flow rate of high-purity argon to 200-300 sccm, start the vacuum pump, evacuate to 50~80 Pa, and heat to 400-600℃ at a rate of 10-15℃ / min, and hold for 10-20 min; S4 maintains the vacuum level of the glass melting furnace and the flow rate of high-purity nitrogen gas, and continues to heat to 1300-1400℃ at a rate of 16-20℃ / min to completely melt the raw material. After clarifying and holding at the temperature, it is cooled to 1200-1300℃ and then homogenized to obtain molten glass. Before discharging in step S5, turn off the vacuum pump and introduce 500-600 sccm of high-purity argon gas for 10-20 minutes until the vacuum degree in the glass melting vacuum furnace is atmospheric pressure. Open the furnace door and pour the molten glass obtained in step S4 into an environment preheated to 400-600℃ for casting and molding. After constant temperature annealing, cool it to room temperature to obtain the high-aluminum-content, high-gloss gadolinium 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 high-yield borosilicate scintillation glass with a wide aluminum content range, in step S1, the Ce... 3+ It is introduced in the form of cerium dioxide and cerium nitrate hexahydrate, barium oxide in the form of barium carbonate, calcium oxide in the form of calcium carbonate, and aluminum oxide in the form of aluminum oxide and aluminum fluoride.

[0017] Preferably, in the aforementioned method for preparing high-yield borosilicate scintillation glass with a wide range of aluminum content, the step S1, wherein the step of uniform mixing is: placing each raw material in an agate mortar and grinding it clockwise for 20-40 minutes using a matching agate grinding rod.

[0018] Preferably, in the aforementioned method for preparing high-yield borosilicate scintillation glass with a wide range of aluminum content, the purity of the raw material in step S1 is 99.99% or higher.

[0019] Preferably, in the aforementioned method for preparing high-yield borosilicate scintillation glass with a wide range of aluminum content, in step S1, the reducing agent is a graphite rod with a size of Φ5-9mm and an amount of 15-25 rods.

[0020] Preferably, in the aforementioned method for preparing high-yield borosilicate scintillation glass with a wide range of aluminum content, in steps S2 and S3, both the small crucible and the large crucible are quartz crucibles, and the cover plate is a quartz cover plate.

[0021] Preferably, in the aforementioned method for preparing high-yield borosilicate scintillation glass with a wide range of aluminum content, the purity of the high-purity argon gas in steps S2 and S5 is ≥99.999%.

[0022] Preferably, in the aforementioned method for preparing high-yield borosilicate scintillation glass with a wide range of aluminum content, in step S4, the clarification and heat preservation time is 1-3 hours, and the homogenization time is 30-40 minutes.

[0023] Preferably, in the aforementioned method for preparing high-yield borosilicate scintillation glass with a wide range of aluminum content, in step S5, the temperature of the isothermal annealing treatment is 400-600℃, and the isothermal annealing treatment time is 2-5h.

[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 comprising a scintillating glass, said scintillating glass being composed of the aforementioned high-yield borosilicate scintillating glass with a wide aluminum content range.

[0025] The objectives of this invention and the technical problems it solves can also be achieved by the following technical measures. This invention proposes an X-ray detection system comprising a scintillation glass, said scintillation glass being composed of the aforementioned high-yield borosilicate scintillation glass with a wide aluminum content range.

[0026] Compared with existing technologies, the high-yield borosilicate scintillation glass with a wide aluminum content range, its preparation method, and its applications described in this invention have the following advantages: The high-aluminum-content, high-brightness-yield gadolinium borosilicate scintillation glass of this invention has a density of 5.8769-6.0047 g / cm³. 3 Between these values, the transmittance at 400 nm is between 83.27% and 86.76%, the decay time is between 54.2% and 68.3 ns, the light yield is between 1184% and 1694 Ph / Mev, the refractive index is between 1.6920% and 1.6985 Ph / Mev, and the coefficient of linear expansion is (88-92)×10⁻⁶. -7 / ℃.

[0027] The high-yield borosilicate scintillation glass with a wide range of aluminum content described in this invention can efficiently convert X-ray energy into photon energy in the field of X-ray imaging, significantly increasing the number of emitted photons per unit X-ray dose. A large number of excited photons can be rapidly transmitted to the photodetector, effectively enhancing the intensity and signal-to-noise ratio of the imaging light signal, reducing the lower limit of X-ray detection, and thus improving the spatial resolution and density resolution accuracy of the imaging system. It is perfectly suited to the application requirements of X-ray imaging scenarios such as high-sensitivity medical imaging and industrial non-destructive testing.

[0028] This invention significantly optimizes raw material costs by introducing a high proportion of alumina as the matrix component of scintillating glass. On one hand, alumina, a mature raw material for industrial-scale production, has a market price far lower than that of rare earth fluorides commonly used in traditional scintillating glass. Replacing some of the expensive rare earth fluorides with a high-alumina content formulation can substantially reduce raw material procurement costs. On the other hand, the high chemical stability and structural regulation of alumina can reduce losses caused by raw material volatilization and corrosion during the melting process, improving raw material utilization and further reducing the overall production cost per unit product. This high-alumina content design effectively solves the industry pain point of high raw material costs for traditional high-yield scintillating glass while ensuring the core performance of the scintillating glass.

[0029] The present invention utilizes the vacuum glass melting environment provided by the glass melting vacuum furnace to remove moisture and gaseous impurities from glass raw materials and the furnace body, suppress volatilization, and improve the uniformity of glass yield and density.

[0030] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below. Attached Figure Description

[0031] Figure 1 These are schematic diagrams illustrating the graphite reducing agent-assisted melting process in Examples 1-8 and Comparative Examples 1-5 of the present invention. The reference numerals are as follows: 1-Large crucible; 2-Crucible cover plate; 3-Small crucible; 4-Graphite rod; 5-Glass feedstock; 6-Quartz sand; Figure 2 These are photographs of the unprocessed raw materials of the scintillation glass obtained in Examples 1-3 of the present invention; Figure 3 The transmittance spectra of the scintillation glass obtained in Examples 1-5 of the present invention are shown. Figure 4 The light yield curves of the scintillation glass obtained in Examples 1-8 of the present invention are shown. Detailed Implementation

[0032] 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 a high-yield borosilicate scintillation glass with a wide aluminum content range, its preparation method, and its application, including its specific implementation methods, structure, features, and effects. 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.

[0033] 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.

[0034] According to some embodiments of the present invention, a high-yield borosilicate scintillation glass with a wide aluminum content range (4-20 wt% aluminum oxide) is provided. The scintillation glass comprises a matrix and luminescent central ions dispersed in the matrix. Through energy transfer between the glass matrices, the luminescence efficiency of Ce ions in the scintillation glass can be significantly improved. The proportions of the components in the matrix, by mass percentage, are: silicon dioxide 3-15%; boron trioxide 4-11%; gadolinium trioxide 50-70%; gadolinium fluoride 6-20%; aluminum oxide 11-20%; gallium oxide 1-2%; barium oxide 2-5%; calcium oxide 0.5-1.5%; scandium oxide 0.3-1.2%; and the luminescent central ion is Ce. 3+ Its content is 2-6%, and the sum of the proportions of the above components is 100%. 3+ It is introduced in the form of cerium dioxide and cerium nitrate hexahydrate, barium oxide in the form of barium carbonate, calcium oxide in the form of calcium carbonate, and aluminum oxide in the form of aluminum oxide and aluminum fluoride.

[0035] In the above technical solution, the roles and contents of each component are selected as follows: Silica (SiO2) acts as a network forging agent in glass, forming the glass network framework. When the silica content is less than 3 wt%, the glass density drops rapidly, failing to meet the high-density requirements of scintillator glasses for high-energy physics detection. When the silica content is greater than 15 wt%, the interconnectivity of silicon-oxygen tetrahedra decreases, reducing the glass's stability. Therefore, this invention selects a silica content between 3 and 15 wt% in the scintillator glass to achieve a glass density greater than 5.8 g / cm³. 3 .

[0036] 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 11 wt%, it can cause phase separation in the glass; while when it is less than 4 wt%, it results in poor thermal stability of the glass.

[0037] 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. When the aluminum oxide content is less than 11 wt%, the glass's chemical stability and mechanical strength are insufficient. However, when the content exceeds 20 wt%, the excessive aluminum oxide content easily leads to glass crystallization, reducing light transmittance; conversely, the absence of aluminum oxide results in insufficient chemical stability and mechanical strength.

[0038] Barium carbonate (BaCO3) is used as a barium source in the preparation of scintillator glass. Its content has a significant impact on the glass properties: a content higher than 5wt% can easily lead to phase separation and crystallization in the glass, reducing transmittance and mechanical stability; a content lower than 2wt% makes it difficult to effectively adjust the glass refractive index and density, affecting the radiation blocking ability and optical signal transmission efficiency.

[0039] Calcium carbonate (CaCO3) serves as a calcium source; it is a network exooxide that, through Ca... 2+ Polarized bridging oxide weakens Si-O / BO bonds, reduces melt viscosity to aid melting, and simultaneously regulates network polymerization degree to improve glass-forming ability. Its content is set within the range of 1-2%. When the calcium oxide content is below 0.5 wt%, insufficient fluxing occurs, and the glass is prone to crystallization; when the calcium oxide content is above 1.5 wt%, the network becomes excessively loose, leading to a decrease in mechanical strength.

[0040] Gallium oxide (Ga2O3) serves as the network exogenous body, Ga 3+ As a network intermediate, it optimizes the network structure, reduces non-bridging oxygen defects, and improves Ce. 3+ The stability and concentration of luminescent centers are crucial for significantly improving the light yield of the glass. The gallium oxide content should not be too high or too low. When the gallium oxide content is below 1 wt%, it leads to more defects in the glass network, increased photon trapping, decreased light output, and a reduction in light yield. When the gallium oxide content is above 2 wt%, it causes phase separation in the glass, damaging the network structure and similarly reducing light yield.

[0041] Scandium oxide (SCO) is the network outer oxide of scintillation glass, and its content is crucial to the control of glass performance: a content higher than 1.2% can easily lead to difficulties in glass melting and an increased risk of crystallization; a content lower than 0.3% cannot fully optimize the energy level of the luminescent center, thus restricting the improvement of light yield.

[0042] Ce 3+ As the luminescent center element in photoluminescence, Ce combines the functions of a functional ion source and structural regulation. 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 component for glass scintillation performance, and their content is set in the range of 2-6 wt%. When the content of cerium dioxide (CeO2) is less than 2 wt%, it will lead to insufficient light yield, while when the content of cerium dioxide is higher than 6 wt%, self-quenching may occur, affecting the luminescence performance.

[0043] Gadolinium fluoride (GdF3) and gadolinium trioxide (Gd2O3) 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 invention improves light yield by co-doping a high content of gadolinium trioxide and an appropriate amount of gadolinium fluoride. The resulting sample significantly increases both glass density and luminous efficiency, better meeting the requirements of high-energy ray and particle detection, as well as high-energy physics and nuclear science experiments. Gadolinium trioxide, with its high atomic number and density, is used to increase the density of scintillator glasses. The gadolinium trioxide content is between 50 and 70 wt%. Below 50 wt%, the glass density is too low; above 70 wt%, the glass is prone to phase separation, resulting in poor glass-forming properties. The gadolinium fluoride content is between 6 and 20 wt%. Below 6 wt%, the glass density is too low; above 20 wt%, it increases raw material costs.

[0044] Testing revealed that the density of the high-yield borosilicate scintillation glass with a wide aluminum content range and its preparation method is between 5.8769 and 6.0047 g / cm³. 3 Between these values, the transmittance at 400nm is between 83.27% and 86.76%, the decay time is between 54.2% and 68.3ns, the light yield is between 1184% and 1694Ph / Mev, and the refractive index is between 1.6920% and 1.6985Ph / Mev.

[0045] According to some embodiments of the present invention, high-yield borosilicate scintillation glass with a wide aluminum content range and a method for preparing the same are also provided, comprising the following steps: Step 1: Weigh the raw materials according to the formula, mix them evenly to obtain the compound material; including: S1 using Si source, B source, Gd source, Al source, Ga source, Ba source, Ca source, Ce source and Sc source as raw materials, mixed evenly according to the mass components of the scintillation glass to obtain raw material powder, and simultaneously weighing the reduction auxiliary material graphite rod to optimize the luminescence performance. The Si source is SiO2 silicon dioxide, the B source is boric acid, the Al source is aluminum oxide, the Ba source is barium carbonate, the Ga source is gallium oxide, the Gd source is gadolinium fluoride and gadolinium oxide, the Ca source is calcium carbonate, and the Ce source is... 3+ The source is cerium dioxide and cerium nitrate hexahydrate, and the Sc source is scandium oxide. The purity of the raw materials is above 99.99%. The graphite rod used as a reducing agent is Φ5mm-Φ9mm in diameter and has a purity of above 99.99%. The graphite rod can consume oxygen in the large crucible, creating a reducing atmosphere inside the crucible. If the diameter of the graphite rod is greater than Φ9mm, the reduction reaction rate is slow, and the Ce in the glass... 4+ Insufficient reduction occurs when the graphite rod diameter is less than Φ5mm, causing it to easily melt and break, resulting in an unstable reducing atmosphere. The amount of graphite rods used is 15-25 rods (10g / rod, 100-300g), which is 1.5-2.5 times the total mass of the glass batch. If the total amount of graphite rods is greater than 2.5 times the total mass of the raw glass batch, the graphite rods are prone to tipping over during glass melting, contaminating the glass. Graphite rods easily cause glass contamination. If the amount of graphite rods is less than 1.5 times the total mass of the raw glass batch, insufficient reducing power in the glass can easily lead to yellowing.

[0046] Step two: Place the uniformly mixed raw materials into a small crucible with a lid. The lid prevents the raw materials from evaporating and escaping during the preheating and melting stages, ensuring accurate glass component ratios and preventing the concentration of luminescent center ions from deviating from the design value, thus degrading scintillator performance. Open the inlet and outlet valves of the vacuum furnace and introduce high-purity argon gas (purity ≥99.999%) for 10-20 minutes. The purpose of argon purging is to remove impurities and moisture from the furnace chamber. If the high-purity argon gas introduction time is less than 10 minutes, the anti-oxidation effect will be insufficient; if the introduction time is more than 20 minutes, it will easily cause glass melt splashing, both of which will degrade the performance of the scintillator glass. The uniformly mixed raw materials are preheated in an annealing furnace at a temperature of 350-450℃ for 0.8-1.2 hours. Preheating temperatures below 350℃ can easily cause crucible cracking or uneven melting of the glass material; preheating temperatures above 450℃ will increase energy consumption and may also cause premature evaporation or deterioration of the glass material. If the preheating time is less than 0.8 hours, the crucible is prone to cracking due to excessively rapid heating rate and temperature difference exceeding the tolerance range, and the glass material is difficult to form a uniform molten state. If the preheating time exceeds 1.2 hours, not only will energy consumption continue to increase, but it will also easily cause volatilization and deterioration of glass material components. The nitrogen flow rate is 500-600 sccm. When the gas flow rate is less than 500 sccm, it will cause incomplete impurity removal, which will affect the purity and optical performance of the scintillation glass. When the nitrogen flow rate is greater than 600 sccm, the excessive flow rate will easily draw in air, which will increase energy consumption.

[0047] Step 3: Place the small crucible containing the batch material into a large crucible sleeve containing the reducing additives. The purpose of the double-layer crucible configuration is to create a reducing atmosphere, inhibit the oxidation of the raw materials, and also to prevent the small crucible inside from breaking and contaminating the melting furnace during the melting process. Its structure is as follows: Figure 1 As shown, both the outer large crucible sleeve 1 and the small crucible 3 are cylindrical. During preparation, firstly, 500 g of high-purity quartz sand 6 is laid at the bottom of the crucible sleeve 1 to form a heat insulation layer. Then, the crucible 3, containing the glass batching material 5, is placed inside. The crucible 3 is equipped with a crucible cover plate 2. Graphite rods 4 are evenly placed in the heat insulation layer between the crucible sleeve 1 and the crucible 3. The large crucible and the small crucible are then placed in a room-temperature glass melting vacuum furnace with a vacuum degree of 1×10⁻⁶. -1 ~5×10 -3 Pa, below 5 × 10 -3 At a vacuum level of 1×10⁻⁶ Pa, excessively low vacuum levels easily lead to oxidation and bubbling; levels above 1×10⁻⁶ Pa are more prone to this. -1 Excessive vacuum at Pa can cause component volatilization. Turn on the circulating cooling water to suppress overheating of the furnace shell, prevent electrical components from aging due to high temperatures, and improve equipment safety and lifespan.

[0048] Step four: After sealing the furnace, adjust the high-purity argon flow rate to 200-300 sccm. A flow rate below 200 sccm makes oxygen isolation difficult, degrading the glass's luminescent properties. A nitrogen flow rate above 300 sccm increases energy consumption. An argon flow rate above 300 sccm causes disturbance in the glass melt. Start the vacuum pump and evacuate to 50-80 Pa. Pressures above 80 Pa exacerbate glass component volatilization, leading to compositional deviation and performance degradation. Pressures below 50 Pa result in insufficient degassing and increased internal porosity defects in the glass. Increase the temperature of the glass melting vacuum furnace to 400-600℃ at a rate of 10-15℃ / min. Temperatures above 600℃ cause component volatilization, leading to glass compositional imbalance. Temperatures below 400℃ result in poor degassing and difficulty in eliminating porosity defects. Hold the temperature for 10-20 minutes to further remove residual moisture and gas from the raw materials. A heating rate of 10-15℃ / min is ideal; a rate greater than 15℃ / min is too fast and can cause material breakage, while a rate less than 10℃ / min is too slow and has low degassing efficiency, both of which affect glass quality. Holding the temperature for too short a time (e.g., less than 10 minutes) will result in incomplete degassing, while holding the temperature for too short or too long a time (e.g., more than 20 minutes) will result in high energy consumption, both of which are detrimental to glass performance.

[0049] Step 5: Maintaining the vacuum level and high-purity nitrogen flow rate in the glass melting furnace, continue heating at a rate of 16-20℃ / min to 1300-1400℃ to completely melt the raw material. Control the glass melting furnace to heat to 1300-1400℃ at a rate of 16-20℃ / min for clarification. If the heating rate is lower than 16℃ / min, the glass melting cycle will be long, and the glass is prone to streaks, affecting the luminescent performance. If the heating rate is higher than 20℃ / min, the glass material will melt unevenly, easily crystallize, and reduce optical uniformity. If the clarification temperature is lower than 1300℃, the glass will not be sufficiently clarified, and streaky bubbles will easily form inside the glass, leading to a decrease in luminescent efficiency. The clarification temperature should not exceed 1400℃, mainly to avoid damage to the heating elements and refractory materials in the furnace due to overheating. Hold the clarification at this temperature for 1-3 hours. A clarification time of less than 1 hour will result in insufficient clarification, while a time longer than 3 hours will lead to the complete consumption of the external reducing agent. After clarifying and holding at a certain temperature, the temperature is lowered to 1200-1300℃ and homogenized for 30-40 minutes to obtain molten glass. Homogenization below 1200℃ will result in incomplete homogenization, leading to structural stress; above 1300℃ will cause excessively high discharge temperature, also generating stress. Homogenization time less than 30 minutes will result in insufficient homogenization; time longer than 40 minutes will cause glass defects.

[0050] Step Six: Before discharging, turn off the vacuum pump and purge with 500-600 sccm of high-purity argon gas (purity ≥99.999%) for 10-20 minutes. If the argon flow rate is below 500 sccm, the inert atmosphere will be insufficient, making the glass prone to oxidation and introducing impurities and defects. If the argon flow rate is above 600 sccm, it will exacerbate component volatilization and increase process energy consumption. If the argon purge time is less than 10 minutes, the inert atmosphere will not be formed, potentially leading to residual oxidizing atmosphere in the furnace and causing Ce2 oxidation. 3+ Oxidized to Ce 4+， To reduce scintillation performance, argon gas is introduced for an excessive time (more than 20 minutes), resulting in argon waste and potential thermal stress due to overcooling. The process continues until the vacuum level in the glass melting furnace reaches atmospheric pressure. The furnace door is then opened, and the molten glass obtained in step S4 is poured into a stainless steel mold preheated to 400-600℃. The mixture undergoes isothermal annealing for 2-5 hours, followed by cooling to room temperature at a rate of 5-8℃ / min, yielding the high-alumina, high-yield gadolinium borosilicate scintillation 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 microcrystalline formation; annealing temperatures below 400℃ can result in difficulty in eliminating internal stress, making the glass prone to cracking and affecting its mechanical properties. Holding times exceeding 5 hours can cause glass deformation and may lead to microcrystalline formation; holding times below 2 hours can result in difficulty in eliminating internal stress, making the glass prone to cracking and affecting its mechanical properties. Regarding the cooling rate, if the cooling rate is >8℃ / min, the internal stress of the glass will concentrate, making it prone to cracking and reducing optical uniformity; if the cooling rate is <5℃ / min, the annealing cycle will be prolonged, the glass will be prone to crystallization, and the luminous efficiency will be reduced.

[0051] In the above technical solution, the high-yield borosilicate scintillation glass with a wide aluminum content range of the present invention possesses excellent high-yield characteristics. After absorbing high-energy rays / particle energy, it can efficiently complete energy conversion, significantly increasing the number of emitted photons per unit energy, enhancing the light signal intensity and signal-to-noise ratio, lowering the detection lower limit, and improving the accuracy and stability of the detector for particle energy measurement, thus meeting the requirements of high-sensitivity detection. The present invention optimizes costs by using a high proportion of alumina as the matrix component, whose price is far lower than that of traditional rare earth fluorides. Replacing some expensive raw materials can reduce procurement costs. Furthermore, alumina can reduce melting losses and improve raw material utilization, further reducing overall costs and solving the pain point of high costs in traditional products. At the same time, the vacuum environment provided by the glass melting vacuum furnace can remove moisture and gaseous impurities from the raw materials and furnace body, suppress volatilization, and improve the density and light yield uniformity of the scintillation glass.

[0052] According to some embodiments of the present invention, a scintillator detector is also provided, which includes a scintillator made of high-yield borosilicate scintillator glass with a wide range of aluminum content as described above.

[0053] According to some embodiments of the present invention, an X-ray detection system is also provided, characterized in that it comprises a scintillator made of high-yield borosilicate scintillator glass with a wide range of aluminum content. High-density scintillator glass offers great potential for advanced X-ray imaging technologies, especially in X-ray CT and compact X-ray detection systems.

[0054] 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.

[0055] The following specific embodiments further illustrate the preparation method of the low-cost, high-performance gadolinium aluminum borosilicate scintillation glass provided by the present invention. Table 1 below lists the mass percentage composition of eight embodiments and five comparative examples of the high-yield borosilicate scintillation glass with a wide aluminum content range and its preparation method according to the present invention.

[0056] The preparation methods of Examples 1-13 and Comparative Examples 1-10 are as follows: According to the mass percentages of the components of the scintillation glass in Examples 1-13 and Comparative Examples 1-10 in Table 1, the raw materials—silica, boron trioxide, gadolinium trioxide, gadolinium fluoride, aluminum trioxide, gallium oxide, barium oxide, calcium oxide, scandium oxide, and cerium dioxide—were mixed uniformly to obtain a mixed raw material powder. The silica raw material was quartz sand, the boron trioxide raw material was boric acid, and the other scintillation glass components were introduced with their corresponding raw materials. The purity of all the above raw materials was 99.99%. Eighteen graphite rods (180g each) with a diameter of Φ6mm and a purity of 99.99% were weighed as a reducing agent.

[0057] Table 1. Composition (wt%) of high-aluminum-content, high-yield gadolinium borosilicate scintillation glasses in Examples 1-13 and Comparative Examples 1-10

[0058]

[0059] The obtained mixed raw material powder was ground and mixed evenly in an agate mortar to obtain a compound. This compound was then dried in a drying oven at 100℃ for 1.5 hours to remove adsorbed moisture. The powder was poured into a small crucible, which was then placed inside a large crucible containing a graphite rod used as a reducing agent. The inlet and outlet valves of the vacuum furnace were opened, and high-purity argon gas (99.999% purity) at 550 sccm was introduced for 10 minutes to purge impurities from the furnace chamber. The small crucible containing the compound was then placed inside the large crucible containing the reducing agent, and the large crucible, along with the small crucible, was placed in a room-temperature glass melting vacuum furnace for melting. Circulating cooling water was turned on. After sealing the furnace, the flow rate of high-purity argon gas was adjusted to 250 sccm, the vacuum pump was started, and a vacuum of 60 Pa was created. The temperature was then increased to 450℃ at a rate of 12℃ / min and held for 15 minutes to further remove residual moisture and gases from the raw materials. Maintaining the vacuum level and high-purity nitrogen flow rate of the glass melting furnace constant, the temperature is increased to 1340℃ at a rate of 18℃ / min to completely melt the raw material. After clarifying and holding at this temperature for 2 hours, the temperature is decreased to 1260℃ at a rate of 10℃ / min, followed by homogenization for 35 minutes to obtain molten glass. Before unloading, the vacuum pump is turned off, and 550 sccm of high-purity argon gas (99.999% purity) is introduced for 10 minutes until the vacuum level in the glass melting furnace reaches atmospheric pressure. The furnace door is then opened, and the molten glass obtained in step S6 is poured into a mold preheated to 450℃ for casting. The mixture is then annealed at a constant temperature for 2.5 hours and cooled to room temperature at a rate of 6℃ / min to obtain the initial product of the high-yield borosilicate scintillating glass with a wide aluminum content range.

[0060] The preparation methods of Examples 1-8 are as follows.

[0061] Weigh 175 g (total weight of raw materials) of each of the components in Examples 1-8 in Table 1 according to their respective mass percentages. Grind and mix the resulting mixed raw material powder evenly in an agate mortar to obtain a compound. Place the compound in a drying oven at 100°C for 1.5 h to remove adsorbed moisture. Pour the compound into a small crucible. Place the small crucible containing the compound into a large crucible sleeve containing 18 graphite rods (Φ6 mm) of reducing auxiliary material. Open the inlet and outlet valves of the vacuum furnace and introduce 550 sccm of high-purity argon gas (purity 99.999%) for 10 min to purge impurities from the furnace chamber. Place the small crucible containing the compound into the large crucible sleeve containing the reducing auxiliary material. Place the large crucible and the small crucible together into a glass melting vacuum furnace at room temperature for melting. Turn on the circulating cooling water. After sealing the furnace, the flow rate of high-purity argon was adjusted to 250 sccm, the vacuum pump was started, and the vacuum was evacuated to 60 Pa. The temperature was then increased to 450 °C at a rate of 12 °C / min and held for 15 min. Maintaining the vacuum furnace pressure of 60 Pa and the high-purity nitrogen flow rate of 250 sccm, the temperature was increased to 1340 °C at a rate of 18 °C / min to completely melt the raw material. After clarifying and holding at that temperature for 2 h, the temperature was decreased to 1260 °C at a rate of 10 °C / min for homogenization treatment for 35 min, resulting in molten glass. Before unloading, the vacuum pump was turned off, and high-purity argon gas (99.999% purity) at 550 sccm was introduced for 10 minutes until the vacuum degree in the glass melting furnace reached atmospheric pressure. The furnace door was then opened, and the resulting molten glass was poured into a preheated furnace at 450°C for casting and molding. The glass was then subjected to constant-temperature annealing for 2.5 hours, followed by cooling to room temperature to obtain the initial high-yield borosilicate scintillation glass preform with a wide aluminum content range. Comparing Examples 1-6, with the increase in alumina content and the decrease in gadolinium fluoride content, the light yield of the scintillation glass increased from 1232 ph / MeV with an alumina content of 4 wt% in Example 7 to 1694 ph / MeV with an alumina content of 17 wt%, achieving a certain degree of increase in light yield with minimal impact on density. Simultaneously, the transmittance at 400 nm decreased from 86.76% in Example 1 to 84.63% in Example 7. The increase in aluminum oxide content and the decrease in gadolinium fluoride content will have a certain impact on the density of the glass. Aluminum oxide has a relatively low molecular weight; as the aluminum oxide content increases, the density of the scintillation glass gradually decreases, from 6.0047 g / cm³ in Example 7. 3 It gradually decreased to 5.9047 g / cm³ in Example 1. 3 This caused a 0.1 g / cm³ effect on the scintillation glass, but the final density remained at 5.9000 g / cm³. 3 The above is within an acceptable range. As the aluminum oxide content continues to increase, localized phase separation and crystallization can easily occur in the glass, reducing its transmittance and luminescent properties. The density of Example 8 is 5.8769 g / cm³.3 The transmittance at 400nm decreased to 83.27%, and the light yield decreased to 1184ph / MeV (see Table 2). The obtained scintillation glass was then cut, surface ground, and polished to form 45×45×10mm scintillation glass.

[0062] The preparation methods of Examples 9-13 are as follows.

[0063] 875g of raw materials (total weight of raw materials) were weighed according to the mass percentage of the components in Example 5 in Table 1. The preparation method was described in the same way as in Examples 1-8. The obtained scintillating glass was cut, surface ground and polished and then processed into 5 pieces of scintillating glass with a diameter of 45×45×10mm, which were named Examples 9-13. The scintillating glass samples of Examples 9-13 were taken, and the relative standard deviation (RSD) of the density value and light yield of the tested glass was calculated according to the formula in (1) to compare its uniformity. The relative standard deviation (SD) of density and the arithmetic mean (x) were calculated by the formula, and the RSD was calculated as the sample standard deviation. The uniformity of the density and light yield of the batch of glass was judged by judging the size of the RSD.

[0064] RSD = SD / x ×100% (1) As shown in Table 2, the densities of Examples 9-13 were 5.9447 g / cm³. 3 5.9458 g / cm 3 5.9432 g / cm 3 5.9456 g / cm 3 and 5.9478 g / cm 3 The RSD of its density was calculated to be 0.028. The light yields of Examples 9-13 were 1281ph / MeV, 1296ph / MeV, 1279ph / MeV, 1282ph / MeV and 1280ph / MeV, and the RSD of their light yields was calculated to be 0.547.

[0065] The preparation methods for Comparative Examples 1-2 are as follows.

[0066] Weigh 175 g (total weight of raw materials) of each of the components in Comparative Examples 1-2 in Table 1 according to their mass percentages. Grind and mix the resulting mixed raw material powder evenly in an agate mortar to obtain a compound. Place the compound in a drying oven at 100℃ for 1.5 h to remove adsorbed moisture. Pour the compound into a small crucible. Place the small crucible containing the compound into a large crucible sleeve containing 18 graphite rods (Φ6mm) of reducing auxiliary material. Open the inlet and outlet valves of the vacuum furnace and introduce 550 sccm of high-purity argon gas (purity 99.999%) for 10 min to purge impurities from the furnace chamber. Place the small crucible containing the compound into the large crucible sleeve containing the reducing auxiliary material. Place the large crucible and the small crucible together into a glass melting vacuum furnace at room temperature for melting. Turn on the circulating cooling water. After sealing the furnace, adjust the high-purity argon flow rate to 250 sccm, start the vacuum pump, evacuate to 60 Pa, and heat to 450 °C at a rate of 12 °C / min, holding for 15 min. Maintaining the glass melting vacuum furnace at 60 Pa and the high-purity nitrogen at 250 sccm, continue heating to 1340 °C at a rate of 18 °C / min to completely melt the raw material. After clarifying and holding at this temperature for 2 h, cool to 1260 °C at a rate of 10 °C / min for homogenization treatment for 35 min to obtain molten glass. Before unloading, the vacuum pump was turned off, and high-purity argon gas (99.999% purity) at 550 sccm was introduced for 10 minutes until the vacuum level in the glass melting furnace reached atmospheric pressure. The furnace door was then opened, and the resulting molten glass was poured into a mold preheated to 450°C for casting. The mixture was then annealed at a constant temperature for 2.5 hours and cooled to room temperature at a rate of 6°C / min to obtain the initial high-yield borosilicate scintillating glass preform with a wide aluminum content range. The obtained scintillating glass preform was then cut, surface-ground, and polished to form 45×45×10mm scintillating glass. In comparison with Examples 1-3, in Comparative Example 1, as the aluminum oxide content increased to 22 wt% while the gadolinium fluoride content decreased to 2 wt%, defects such as glass phase separation and crystallization worsened, resulting in a decrease in the luminous yield of the scintillating glass to 977 ph / MeV and a decrease in density to 5.8427 g / cm³. 3 The transmittance at 400 nm decreased to 79.02%. For Comparative Example 2, compared to Examples 1-8, the alumina content was reduced to 3 wt%, and the gadolinium fluoride content increased to 21 wt%. The high gadolinium fluoride content significantly increased the glass density to 6.0098 g / cm³. 3 The light yield decreased to 10¹⁸ ph / MeV, the transmittance at 400 nm decreased to 83.12%, and the high amount of gadolinium fluoride significantly increased the manufacturing cost of scintillation glass, as shown in Table 2.

[0067] The preparation method of Comparative Example 3 is as follows.

[0068] Weigh 175 g of raw materials (total weight of raw materials) according to the mass percentage of the three components in Comparative Example 1. Grind and mix the resulting mixed raw material powder evenly in an agate mortar to obtain a compound. Place it in a drying oven at 100℃ for 1.5 h to remove adsorbed moisture. Pour it into a small crucible. Place the small crucible containing the compound into a large crucible sleeve containing graphite rods for reducing the material. Select 18 graphite rods with a diameter of 10 mm. Open the inlet and outlet valves of the vacuum furnace and introduce 550 sccm of high-purity argon gas (purity of 99.999%) for 10 min to purge impurities in the furnace chamber. Place the small crucible containing the compound into the large crucible sleeve containing the reducing material, and place the large crucible together with the small crucible into a glass melting vacuum furnace at room temperature for melting. Turn on the circulating cooling water. After sealing the furnace, the flow rate of high-purity argon was adjusted to 250 sccm, the vacuum pump was started, and the vacuum was evacuated to 60 Pa. The temperature was then increased to 450 °C at a rate of 12 °C / min and held for 15 min. Maintaining the vacuum furnace pressure of 60 Pa and the high-purity nitrogen flow rate of 250 sccm, the temperature was increased to 1340 °C at a rate of 18 °C / min to completely melt the raw material. After clarifying and holding at that temperature for 2 h, the temperature was decreased to 1260 °C at a rate of 10 °C / min for homogenization treatment for 35 min, resulting in molten glass. Before unloading, the vacuum pump is turned off, and high-purity argon gas (99.999% purity) at 550 sccm is introduced for 10 minutes until the vacuum level in the glass melting furnace reaches atmospheric pressure. The furnace door is then opened, and the resulting molten glass is poured into a mold preheated to 450°C for casting. The mixture is then subjected to constant-temperature annealing for 2.5 hours, followed by cooling to room temperature at a rate of 6°C / min. This yields the initial blank of the high-yield borosilicate scintillating glass with a wide aluminum content range. The resulting initial scintillating glass is then cut, surface-ground, and polished to form 45×45×10mm scintillating glass pieces. Compared with Example 2, Comparative Example 3 maintained the same glass composition and melting process, but increased the diameter of the graphite rod to Φ10mm. The excessively large diameter of the graphite rod used in the glass unloading stage resulted in a significant reduction in combustion efficiency, making it difficult to form an effective reducing atmosphere and easily causing the high-temperature glass melt to be oxidized. As a result, the glass light yield dropped to 969ph / MeV, and the transmittance at 400nm dropped to 83.63%, as shown in Table 2.

[0069] The preparation method of Comparative Example 4 is as follows.

[0070] Weigh 175 g of raw materials (total weight of raw materials) according to the mass percentage of the four components in Comparative Example 1 in Table 1. Grind and mix the resulting mixed raw material powder evenly in an agate mortar to obtain a compound. Place it in a drying oven at 100℃ for 1.5 h to remove adsorbed moisture. Pour it into a small crucible. Place the small crucible containing the compound into a large crucible sleeve containing graphite rods for reducing the material. Select 13 graphite rods with a diameter of 6 mm. Open the inlet and outlet valves of the vacuum furnace and introduce high-purity argon gas (purity of 99.999%) at 550 sccm for 10 min to purge impurities from the furnace chamber. Place the small crucible containing the compound into the large crucible sleeve containing the reducing material, and place the large crucible together with the small crucible into a glass melting vacuum furnace at room temperature for melting. Turn on the circulating cooling water. After sealing the furnace, the flow rate of high-purity argon was adjusted to 250 sccm, the vacuum pump was started, and the vacuum was evacuated to 60 Pa. The temperature was then increased to 450 °C at a rate of 12 °C / min and held for 15 min. Maintaining the vacuum furnace pressure of 60 Pa and the high-purity nitrogen flow rate of 250 sccm, the temperature was increased to 1340 °C at a rate of 18 °C / min to completely melt the raw material. After clarifying and holding at that temperature for 2 h, the temperature was decreased to 1260 °C at a rate of 10 °C / min for homogenization treatment for 35 min, resulting in molten glass. Before unloading, the vacuum pump was turned off, and high-purity argon gas (99.999% purity) at 550 sccm was introduced for 10 minutes until the vacuum level in the glass melting furnace reached atmospheric pressure. The furnace door was then opened, and the resulting molten glass was poured into a mold preheated to 450°C for casting. The mixture was then annealed at a constant temperature for 2.5 hours and cooled to room temperature at a rate of 6°C / min to obtain the initial blank of the high-yield borosilicate scintillating glass with a wide aluminum content range. The obtained initial scintillating glass blank was then cut, surface-ground, and polished to form scintillating glass pieces of 45×45×10mm. In Comparative Example 4, the glass composition and melting process remained consistent with Example 2. However, if the number of graphite rods was insufficient during glass unloading, it was difficult to form a continuous and dense reducing atmosphere. The high-temperature molten glass easily oxidized upon contact with air, resulting in a glass yield reduction to 977 ph / MeV and a transmittance of 82.88% at 400nm (see Table 2).

[0071] The preparation method of Comparative Example 5 is as follows.

[0072] Weigh 175 g of raw materials (total weight of raw materials) according to the mass percentage of the five components in Comparative Example 5 in Table 1. Grind and mix the resulting mixed raw material powder evenly in an agate mortar to obtain a compound. Place it in a drying oven at 100℃ for 1.5 h to remove adsorbed moisture. Pour it into a small crucible. Place the small crucible containing the compound into a large crucible sleeve containing 18 graphite rods (Φ6mm) of reducing auxiliary material. Open the inlet and outlet valves of the vacuum furnace and introduce 550 sccm of high-purity argon gas (purity of 99.999%) for 10 min to purge impurities in the furnace chamber. Place the small crucible containing the compound into the large crucible sleeve containing the reducing auxiliary material. Place the large crucible together with the small crucible into a glass melting vacuum furnace at room temperature for melting. Turn on the circulating cooling water. After sealing the furnace, the flow rate of high-purity argon was adjusted to 150 sccm, the vacuum pump was started, and the vacuum was evacuated to 60 Pa. The temperature was then increased to 450 °C at a rate of 12 °C / min and held for 15 min. Maintaining the glass melting vacuum furnace at 60 Pa and the high-purity nitrogen at 150 sccm, the temperature was increased to 1340 °C at a rate of 18 °C / min to completely melt the raw material. After clarifying and holding at that temperature for 2 h, the temperature was decreased to 1260 °C at a rate of 10 °C / min for homogenization treatment for 35 min, resulting in molten glass. Before unloading, the vacuum pump was turned off, and high-purity argon gas (99.999% purity) at 550 sccm was introduced for 10 minutes until the vacuum level in the glass melting furnace reached atmospheric pressure. The furnace door was then opened, and the resulting molten glass was poured into a mold preheated to 450°C for casting. The mixture was then annealed at a constant temperature for 2.5 hours and cooled to room temperature at a rate of 6°C / min to obtain the initial high-yield borosilicate scintillation glass preform with a wide aluminum content range. The obtained scintillation glass preform was then cut, surface-ground, and polished to form 45×45×10mm scintillation glass. In Comparative Example 5, the glass composition and process were basically the same as in Example 2. However, during the vacuum melting process, the low nitrogen flow rate of 150 sccm could not completely remove oxygen from the furnace. Oxygen reacted with the high-temperature glass, causing a significant decrease in its light yield. Therefore, the glass light yield dropped to 980 ph / MeV, and the transmittance at 400 nm dropped to 81.72% (see Table 2).

[0073] The preparation methods for Comparative Examples 6-10 are as follows.

[0074] Weigh 875g of raw materials (total weight) according to the mass percentages of the components in Example 5 of Table 1. Grind and mix the resulting mixed raw material powder evenly in an agate mortar to obtain a compound. Place the compound in a drying oven at 100℃ for 1.5h to remove adsorbed moisture. Pour the compound into a small crucible. Place the small crucible containing the compound into a large crucible sleeve containing 18 graphite rods (Φ6mm) of reducing agent. Place the small crucible containing the compound into the large crucible sleeve containing the reducing agent. Place the large crucible and the small crucible together in a vacuum glass melting furnace at room temperature for melting. Do not pass gas or apply vacuum. Heat to 450℃ at a rate of 12℃ / min and hold for 15min. Continue heating to 1340℃ at a rate of 18℃ / min to completely melt the raw materials. After clarifying and holding at this temperature for 2h, cool to 1260℃ at a rate of 10℃ / min for homogenization treatment for 35min to obtain a molten glass. The obtained molten glass was poured into a preheated container at 450°C for casting and molding. It was then subjected to constant-temperature annealing for 2.5 hours, followed by cooling to room temperature to obtain the initial product of the high-yield borosilicate scintillation glass preform with a wide aluminum content range. The obtained scintillation glass preform was cut, surface-ground, and polished into five 45×45×10mm scintillation glass pieces, named Comparative Examples 6-10. The scintillation glass samples of Comparative Examples 6-10 were taken, and their density values ​​and relative standard deviations (RSD) of light yield were calculated according to formula (1) to compare their uniformity. The results are shown in Table 2. The densities of Comparative Examples 6-10 were 5.9569 g / cm³. 3 5.9384 g / cm 3 5.9263 g / cm 3 5.9668 g / cm 3 and 5.9025 g / cm 3 The calculated RSD of its density was 0.428. The light yields obtained in Examples 9-13 were 1103 ph / MeV, 1109 ph / MeV, 1100 ph / MeV, 1136 ph / MeV, and 1084 ph / MeV, with a calculated RSD of 1.713. Compared to Examples 9-13, the density and light yield uniformity were significantly lower.

[0075] Table 2 Corresponding properties of the glasses in Examples 1-13 and Comparative Examples 1-10

[0076] The densities of the glass samples in the embodiments and comparative examples of this invention were measured using an MH-1200F balance manufactured by Qunlong Instruments Co., Ltd. The measurement principle was Archimedes' displacement method, and deionized water was used in all tests. The embodiments and comparative examples of this invention used a U-4100 ultraviolet-visible spectrophotometer from Hitachi, Japan, employing double-sided polished transparent scintillation glass for testing. The embodiments and comparative examples of this invention used a PMT XP2020 photocathode photomultiplier tube for attenuation time testing. The light yields in the embodiments and comparative examples of this invention were measured in γ-ray transmission mode using a 662K cv137Cs source. The embodiments and comparative examples of this invention used a WYA-2W Abbe refractometer for refractive index testing. The embodiments and comparative examples of this invention used a DIL 402EP thermal dilatometer for coefficient of thermal expansion testing.

[0077] The scintillation glass compositions of Examples 1-13 and Comparative Examples 1-10 are shown in Table 1, and the density, refractive index, transmittance, light yield, coefficient of linear expansion, and decay time are shown in Table 2.

[0078] Figure 1 The accompanying diagrams illustrate the graphite reducing agent-assisted melting process of Examples 1-13 and Comparative Examples 1-10 of the present invention. Figure 1 Marking descriptions: 1-Large crucible; 2-Crucible lid; 3-Small crucible; 4-Graphite rod; 5-Glass feed; 6-Quartz sand, its structure is as follows: Figure 1 As shown, both the outer large crucible sleeve 1 and the small crucible 3 have a cylindrical structure. During preparation, firstly, 500 g of high-purity quartz sand 6 is laid at the bottom of the crucible sleeve 1 to form a high-purity quartz sand insulation layer. Then, the crucible 3, containing the glass compound 5, is placed on top of it, and the crucible 3 is equipped with a crucible cover plate 2. Graphite rods 4, the reduction auxiliary material, are evenly placed in the high-purity quartz sand insulation layer between the crucible 3 and the crucible sleeve 1. Figure 2 These are photographs of the unprocessed raw materials of the scintillation glass obtained in Examples 1-3 of the present invention. The raw materials are all uniformly dense and without obvious bubbles, streaks, or crystallization defects. Figure 3 The transmittance curves of the scintillation glass obtained in Examples 1-5 of the present invention are shown in the figure. As can be seen from the figure, as the aluminum oxide content decreases, the glass can maintain a high transmittance of 85-87% at 400nm. Figure 4 The light yield curves of the scintillation glass obtained in Examples 1-8 of the present invention show that as the aluminum oxide content decreases, the light yield of the glass decreases from 1694ph / MeV to 1184ph / MeV.

[0079] The high-yield borosilicate scintillation glass with aluminum content described in this invention is applied to X-ray detection systems. These systems are core equipment for advanced X-ray imaging, possessing high sensitivity and high-resolution X-ray detection capabilities. The scintillation glass from Example 1 is selected, with a density of 5.9047 g / cm³. 3 The photoluminescence quantum yield reached 75.1%, and the spatial resolution reached 10 lp mm. −1 The decay time is 62.1 ns. It is processed into a 20mm×20mm×5mm cube and the surface is ground and polished. Several units are arranged in an array to construct the detection module.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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 high-yield borosilicate scintillation glass with a wide range of aluminum content, characterized in that, The scintillation glass comprises a matrix and luminescent central ions dispersed in the matrix. The high-yield borosilicate scintillation glass with a wide aluminum content range comprises a matrix and luminescent central ions dispersed in the matrix. The proportions of each component in the matrix by mass percentage are as follows: silicon dioxide 3-15%; boron trioxide 4-11%; gadolinium trioxide 50-70%; gadolinium fluoride 6-20%; aluminum trioxide 4-20%; gallium oxide 1-3%; barium oxide 2-5%; calcium oxide 0.5-1.5%; scandium oxide 0.3-1.2%. The content of the luminescent central ions is 2-9%, and the sum of the proportions of the above components is 100%.

2. The high-yield borosilicate scintillation glass with a wide aluminum content range as described in claim 1, characterized in that, The luminescent central ion is Ce. 3+ .

3. The high-yield borosilicate scintillation glass with a wide aluminum content range as described in claim 1, characterized in that, The high-yield borosilicate scintillator glass with a wide aluminum content range has a density of 5.8769-6.0047 g / cm³. 3 Between these values, the transmittance at 400nm is between 83.27% and 86.76%, and the decay time is between 54.2% and 68.3ns.

4. The high-yield borosilicate scintillation glass with a wide aluminum content range as described in claim 1, characterized in that, The high-yield borosilicate scintillating glass with a wide range of aluminum content has an optical yield between 1184 and 1694 Ph / Mev and a refractive index between 1.6920 and 1.6985 Ph / Mev.

5. A method for preparing a high-yield borosilicate scintillation glass with a wide range of aluminum content, characterized in that, Includes the following steps: S1 uses Si, B, Gd, Al, Ga, Ba, Ca, Ce and Sc sources as raw materials. The raw materials are weighed and mixed evenly according to the formula to obtain raw material powder, which is dried at 90-100℃ for 1-2 hours. At the same time, the reducing auxiliary materials are weighed. S2 Place the uniformly mixed raw materials from step S1 into a small crucible with a cover plate; open the inlet and outlet valves of the vacuum furnace and introduce 500-600 sccm of high-purity argon gas for 10 minutes. S3. Place the small crucible containing the batch material into the large crucible sleeve containing the reducing auxiliary material, and place the large crucible together with the small crucible into a glass melting vacuum furnace at room temperature for melting, and turn on the circulating cooling water; after sealing the furnace body, adjust the flow rate of high-purity argon to 200-300 sccm, start the vacuum pump, evacuate to 50~80 Pa, and heat to 400-600℃ at a rate of 10-15℃ / min, and hold for 10-20 min; S4 maintains the vacuum level of the glass melting furnace and the flow rate of high-purity nitrogen gas, and continues to heat to 1300-1400℃ at a rate of 16-20℃ / min to completely melt the raw material. After clarifying and holding at the temperature, it is cooled to 1200-1300℃ and then homogenized to obtain molten glass. Before discharging S5, turn off the vacuum pump and introduce 500-600 sccm of high-purity argon gas for 10-20 minutes until the vacuum level in the glass melting vacuum furnace is atmospheric pressure, then open the furnace door. S6 The molten glass obtained in step S4 is poured into an environment preheated to 400-600℃ for casting and molding, subjected to constant temperature annealing, and then cooled to room temperature to obtain the high aluminum content, high light yield gadolinium borosilicate scintillation glass.

6. The method for preparing high-yield borosilicate scintillation glass with a wide aluminum content range as described in claim 5, characterized in that, In step S1, the Ce 3+ The raw materials are introduced in the form of cerium dioxide and cerium nitrate hexahydrate, barium oxide in the form of barium carbonate, calcium oxide in the form of calcium carbonate, and aluminum oxide in the form of aluminum oxide and aluminum fluoride. The step of uniform mixing is as follows: place each raw material in an agate mortar and grind it clockwise for 20-40 minutes using a matching agate grinding rod. The purity of the raw materials is above 99.9%. The reducing agent is a graphite rod with a size of Φ5-9mm, and the amount used is 15-25 rods.

7. The method for preparing high-yield borosilicate scintillation glass with a wide aluminum content range as described in claim 5, characterized in that, In steps S2 and S4, the crucibles are quartz crucibles and the cover plates are quartz cover plates; in steps S2 and S5, the purity of the high-purity argon gas is ≥99.999%.

8. The method for preparing high-yield borosilicate scintillation glass with a wide aluminum content range as described in claim 5, characterized in that, In step S4, the clarification and heat preservation time is 1-3 hours, and the homogenization time is 30-40 minutes.

9. The method for preparing high-yield borosilicate scintillation glass with a wide aluminum content range as described in claim 5, characterized in that, In step S5, the temperature of the isothermal annealing treatment is 400-600℃, and the isothermal annealing treatment time is 1-4h.

10. A scintillator detector, characterized in that, It includes a scintillator, which is made of high-yield borosilicate scintillator glass with a wide range of aluminum content as described in any one of claims 1-4.

11. An X-ray detection system, characterized in that, It includes a scintillator, which is made of high-yield borosilicate scintillator glass with a wide range of aluminum content as described in any one of claims 1-4.

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