Glass scintillator material with x-ray response performance and preparation method and application thereof

Abstract

The application belongs to the technical field of glass scintillator material preparation, and provides a glass scintillator material with X-ray response performance and a preparation method and application thereof. Boron oxide, aluminum oxide, calcium oxide, sodium carbonate, a manganese source, sodium bromide and stannous oxide are mixed and reacted to obtain a molten glass solution; the molten glass solution is cooled on a preheated mold to obtain a glass precursor; the glass precursor is sequentially annealed, polished and heat-treated to obtain the glass scintillator material with X-ray response performance. The method has an induced self-crystallization process, can avoid time-consuming and laborious regulation of the complex nucleation thermodynamics and kinetics process of the traditional microcrystalline glass scintillator material, and can also avoid the addition of a Cs source, thereby reducing the production cost, preparing the glass scintillator material with large area, high stability and excellent performance, enabling the glass scintillator material to serve in extreme environments for a long time, and expanding the application range of the glass scintillator material.

Description

Technical Field

[0001] This invention relates to the field of glass scintillator material preparation technology, and in particular to a glass scintillator material with X-ray response properties, its preparation method and application. Background Technology

[0002] Currently used classical scintillators (CsI:Tl, CdS, CsPbBr3) are limited by their poor stability and can only operate in relatively mild environments, such as medical imaging, industrial imaging, and security inspections, where they operate at room temperature, low humidity, and low doses. However, key national sectors such as aviation, maritime, and nuclear industries urgently require X-ray detectors that can operate in extremely harsh environments, necessitating the development of a scintillator capable of operating in extreme conditions (high temperature, high humidity, high light intensity, and high radiation).

[0003] Scintillation glasses, due to their dense and stable glass network structure, possess stability unmatched by other forms of scintillators (scintillation crystals, scintillation organics, scintillation ceramics), and have therefore received extensive research and attention from scholars both domestically and internationally. Currently developed scintillation glasses are mainly divided into perovskite microcrystalline glasses and rare-earth ion microcrystalline glasses. Although their stability issues have been resolved, the following four problems still need to be addressed to ensure their service in extreme environments: 1) Difficulty in uniform large-area preparation, involving complex nucleation thermodynamics and growth kinetics, making large-area uniform nucleation and growth challenging; 2) Low light yield, characterized by severe self-absorption effects (Pb-based), electron transition forbidden effects (ff transition rare-earth-based), energy loss due to defect traps, and narrow emission spectrum full width at half maximum (FWHM), all detrimental to light emission; 3) Poor resolution, due to the significant difference in composition between the glass phase and the luminescent phase in the scintillation glass, leading to excessive refractive index mismatch and exacerbating refraction and scattering of the light path; 4) High cost, containing expensive elements such as alkali metal Cs and rare-earth metals Ce and Tb.

[0004] In summary, optimizing large-area fabrication processes, increasing light yield, improving resolution, and reducing costs are pressing issues that need to be addressed in this field. Providing a truly luminescent glass X-ray detection material that can operate for extended periods in extreme environments is essential. Summary of the Invention

[0005] In view of this, the present invention provides a glass scintillator material with X-ray response performance, its preparation method and application, to solve the problem that existing classical scintillators cannot be used in extreme and harsh environments, and that existing scintillating glasses, although highly stable, have problems such as difficulty in large-area preparation, low light yield, poor resolution and high cost.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention provides a method for preparing a glass scintillator material with X-ray responsive properties, comprising the following steps:

[0008] (1) Mix boron oxide, aluminum oxide, calcium oxide, sodium carbonate, manganese source, sodium bromide and stannous oxide and react to obtain a molten glass solution;

[0009] (2) Cool the molten glass solution on a preheated mold to obtain a glass precursor;

[0010] (3) The glass precursor is annealed, polished and heat-treated in sequence to obtain a glass scintillator material with X-ray response performance.

[0011] Preferably, in step (1), the mass ratio of boron oxide, aluminum oxide, calcium oxide, sodium carbonate, manganese source, sodium bromide and stannous oxide is 5-7:3-4:1.0-1.5:0.1-0.4:0.2-3:2-5:0.1-0.5.

[0012] Preferably, the manganese source in step (1) includes one or more of manganese bromide, manganese chloride, and manganese oxide.

[0013] Preferably, the reaction temperature in step (1) is 1200-1400℃ and the reaction time is 10-30 minutes.

[0014] Preferably, the temperature of the preheated mold in step (2) is 400-450°C.

[0015] Preferably, the annealing temperature in step (3) is 400-450°C and the annealing time is 2-5 hours.

[0016] Preferably, the heat treatment temperature in step (3) is 450-650°C and the heat treatment time is 5-25 hours.

[0017] The present invention also provides a glass scintillator material with X-ray responsive properties prepared by the above-mentioned method for preparing glass scintillator materials with X-ray responsive properties.

[0018] The present invention also provides an application of the above-mentioned glass scintillator material with X-ray response properties as an X-ray detection material.

[0019] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] 1. This invention employs a high-temperature melting and quenching method, utilizing the uniform thermal diffusion of ions in molten glass at high temperatures to form nucleation sites during the cooling process, inducing a nucleation process assisted by glass components (induced self-crystallization process). This avoids the time-consuming and laborious process of controlling the complex nucleation thermodynamics and kinetics of traditional microcrystalline glass scintillator materials, as well as the uneconomical addition of Cs sources. It can realize the preparation of large-area X-ray detection materials and reduce production costs. Furthermore, the preparation method described in this invention has the characteristics of simple operation, short time, and controllable thickness, which can greatly promote the industrial production of large-area X-ray detection materials.

[0021] 2. The preparation method described in this invention can produce X-ray detection materials with a detection limit below 159.5 μGy / s, a light yield above 3000 Photons / MeV, and a resolution of not less than 11.2 lp / mm. Compared to traditional glass-ceramics, the preparation method of the X-ray detection material described in this invention has an induced self-crystallization process, allowing it to emit light without heat treatment. Simultaneously, it ensures that the luminescent phase is uniformly dispersed within the glass, guaranteeing uniform luminescence. This method can produce X-ray detection materials with an area as high as 50.2 cm². 2 Large-area and highly stable glass scintillator materials with X-ray responsive properties enable them to serve for extended periods in extreme environments, expanding the application range of X-ray detection materials.

[0022] 3. The preparation method described in this invention enables the continuous and adjustable luminescence of the X-ray detection material, and the conversion from yellow light to orange light can be achieved by changing the concentration of luminescent ions (manganese ions). Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0024] Figure 1 The XRD patterns are of the glass scintillator materials of Examples 1-5 and Comparative Example 1.

[0025] Figure 2 The images shown are physical representations of the glass scintillator materials used in Examples 1-5. Figure 2 In the image, 'a' represents the actual object under natural light. Figure 2 In the image, b represents the actual object under ultraviolet light. Figure 2 In the image, 'c' represents the actual object under X-rays.

[0026] Figure 3 The images show the radiative emission patterns of the glass scintillator materials in Examples 1-5.

[0027] Figure 4 This is a high-temperature imaging image of the glass scintillator material with X-ray response properties in Example 3. Detailed Implementation

[0028] This invention provides a method for preparing a glass scintillator material with X-ray responsive properties, comprising the following steps:

[0029] (1) Mix boron oxide, aluminum oxide, calcium oxide, sodium carbonate, manganese source, sodium bromide and stannous oxide and react to obtain a molten glass solution;

[0030] (2) Cool the molten glass solution on a preheated mold to obtain a glass precursor;

[0031] (3) The glass precursor is annealed, polished and heat-treated in sequence to obtain a glass scintillator material with X-ray response performance.

[0032] In this invention, the preferred mass ratio of boron oxide, aluminum oxide, calcium oxide, sodium carbonate, manganese source, sodium bromide, and stannous oxide in step (1) is 5-7:3-4:1.0-1.5:0.1-0.4:0.2-3:2-5:0.1-0.5, more preferably 5.5-6:3.2-3.8:1.1-1.3:0.2-0.3:1.0-2.5:2.5-4.0:0.2-0.3, and even more preferably 5.85:3.26:1.12:0.21:1.32:3.09:0.27.

[0033] In this invention, the manganese source in step (1) preferably includes one or more of manganese bromide, manganese chloride, and manganese oxide.

[0034] In this invention, the reaction temperature in step (1) is preferably 1200-1400°C, more preferably 1250-1350°C, and even more preferably 1300°C. The reaction time is preferably 10-30 minutes, more preferably 15-25 minutes, and even more preferably 20 minutes.

[0035] The temperature of the preheating mold in step (2) of the present invention is preferably 400-450°C, more preferably 410-430°C, and even more preferably 420°C.

[0036] In this invention, the preheating mold includes a copper mold or a graphite mold.

[0037] The annealing temperature in step (3) of the present invention is 400-450°C, more preferably 410-430°C, and even more preferably 420°C. The annealing time is 2-5 hours, more preferably 2.5-4 hours, and even more preferably 3 hours. Annealing can eliminate the internal stress of the glass and prevent it from breaking.

[0038] In this invention, after the annealing process is completed, the glass precursor is also cut into the required shape and thickness.

[0039] In this invention, the polishing operation is preferably performed as follows: the cut glass is fixed on a polishing machine equipped with sandpaper of different grits (400-8000 grit) for polishing, with each grit requiring 5 minutes of polishing. The polished glass is then transferred to a polishing machine equipped with a fine-grit cloth, and diamond abrasive paste of different grits (8000-30000 grit) is applied to the cloth for polishing, with each grit requiring 10 minutes of polishing, to obtain a transparent glass body.

[0040] In this invention, sandpaper with different mesh counts (400-8000 mesh) includes 400, 800, 1200, 1500, 2000, 3000, 5000, and 8000 mesh; and diamond abrasive paste with different high mesh counts (8000-30000 mesh) includes 8000, 15000, and 30000 mesh.

[0041] The heat treatment temperature in step (3) of the present invention is 450-650°C, more preferably 500-600°C, and even more preferably 550°C. The heat treatment time is 5-25 hours, more preferably 15-22 hours, and even more preferably 20 hours. The heat treatment can fully eliminate internal defects in the glass.

[0042] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0043] Example 1:

[0044] Weigh out 5.85g boron oxide, 3.26g aluminum oxide, 1.12g calcium oxide, 0.21g sodium carbonate, 0.21g manganese bromide, 3.09g sodium bromide, and 0.27g stannous oxide. Add these to a 16cm diameter ceramic mortar and mix thoroughly. Place the resulting powder in a high-temperature muffle furnace preheated to 1300℃ and heat for 20 minutes to fully mix and react, obtaining a molten glass solution. Then, pour the molten glass solution onto a graphite mold preheated to 420℃ to cool and solidify, obtaining a glass precursor. Next, place the glass precursor in a low-temperature muffle furnace and heat it to 420℃, maintaining the temperature for 3 hours for annealing. Finally, cut the annealed glass to the required thickness. The glass was then polished sequentially on polishing machines with mesh sizes of 400, 800, 1200, 1500, 2000, 3000, 5000, and 8000 mesh, each polishing lasting 5 minutes. Afterward, the glass was transferred to a polishing machine fitted with a felt cloth, and diamond abrasive paste with mesh sizes of 8000, 15000, and 30000 mesh was applied to the felt cloth for polishing, each polishing lasting 10 minutes. Finally, the polished glass was placed in a low-temperature muffle furnace, heated to 550°C, and held for 20 hours for heat treatment to obtain a 0.5% concentration of glass scintillator material with X-ray responsive properties, denoted as 0.5%MnBr2 or Al4B2O9:0.5%MnBr2.

[0045] Example 2

[0046] Weigh out 5.85g boron oxide, 3.26g aluminum oxide, 1.12g calcium oxide, 0.21g sodium carbonate, 0.43g manganese bromide, 3.09g sodium bromide, and 0.27g stannous oxide, and add them to a 16cm diameter ceramic mortar. Mix thoroughly until homogeneous. Place the resulting powder in a high-temperature muffle furnace preheated to 1300℃ and heat for 20 minutes to fully mix and react, obtaining a molten glass solution. Then, pour the molten glass solution onto a copper mold preheated to 420℃ to cool and solidify, obtaining a glass precursor. Next, place the glass precursor in a low-temperature muffle furnace and heat it to 420℃, maintaining the temperature for 3 hours for annealing. Finally, cut the annealed glass to the required thickness. The glass was then polished sequentially on polishing machines with mesh sizes of 400, 800, 1200, 1500, 2000, 3000, 5000, and 8000 mesh, each polishing lasting 5 minutes. Afterward, the glass was transferred to a polishing machine fitted with a felt cloth, and diamond abrasive paste with mesh sizes of 8000, 15000, and 30000 mesh was applied to the felt cloth for polishing, each polishing lasting 10 minutes. Finally, the polished glass was placed in a low-temperature muffle furnace, heated to 550°C, and held for 20 hours for heat treatment to obtain a 1.0% concentration of glass scintillator material with X-ray responsive properties, denoted as 1.0%MnBr2 or Al4B2O9:1.0%MnBr2.

[0047] Example 3

[0048] Weigh out 5.85g boron oxide, 3.26g aluminum oxide, 1.12g calcium oxide, 0.21g sodium carbonate, 1.29g manganese bromide, 3.09g sodium bromide, and 0.27g stannous oxide, and add them to a 16cm diameter ceramic mortar. Mix thoroughly until homogeneous. Place the resulting powder in a high-temperature muffle furnace preheated to 1300℃ and heat for 20 minutes to fully mix and react, obtaining a molten glass solution. Then, pour the molten glass solution onto a copper mold preheated to 420℃ to cool and solidify, obtaining a glass precursor. Next, place the glass precursor in a low-temperature muffle furnace and heat it to 420℃, maintaining the temperature for 3 hours for annealing. Finally, cut the annealed glass to the required thickness. The glass was then polished sequentially on polishing machines with mesh sizes of 400, 800, 1200, 1500, 2000, 3000, 5000, and 8000 mesh, each polishing lasting 5 minutes. Afterward, the glass was transferred to a polishing machine fitted with a soft cloth, and diamond abrasive paste with mesh sizes of 8000, 15000, and 30000 mesh was applied to the cloth for polishing, each polishing lasting 10 minutes. Finally, the polished glass was placed in a low-temperature muffle furnace, heated to 550°C, and held for 20 hours for heat treatment to obtain a 3.0% concentration glass scintillator material with X-ray responsive properties, denoted as 3.0%MnBr2 or Al4B2O9:3.0%MnBr2.

[0049] Example 4

[0050] Weigh out 5.85g boron oxide, 3.26g aluminum oxide, 1.12g calcium oxide, 0.21g sodium carbonate, 2.15g manganese bromide, 3.09g sodium bromide, and 0.27g stannous oxide. Add these to a 16cm diameter ceramic mortar and mix thoroughly. Place the resulting powder in a high-temperature muffle furnace preheated to 1300℃ and heat for 20 minutes to fully mix and react, obtaining a molten glass solution. Then, pour the molten glass solution onto a graphite mold preheated to 420℃ to cool and solidify, obtaining a glass precursor. Next, place the glass precursor in a low-temperature muffle furnace and heat it to 420℃, maintaining the temperature for 3 hours for annealing. Finally, cut the annealed glass to the required thickness. The glass was then polished sequentially on polishing machines with mesh sizes of 400, 800, 1200, 1500, 2000, 3000, 5000, and 8000 mesh, each polishing lasting 5 minutes. Afterward, the glass was transferred to a polishing machine fitted with a felt cloth, and diamond abrasive paste with mesh sizes of 8000, 15000, and 30000 mesh was applied to the felt cloth for polishing, each polishing lasting 10 minutes. Finally, the polished glass was placed in a low-temperature muffle furnace, heated to 550°C, and held for 20 hours for heat treatment to obtain a 5.0% concentration glass scintillator material with X-ray responsive properties, denoted as 5.0%MnBr2 or Al4B2O9:5.0%MnBr2.

[0051] Example 5

[0052] Weigh out 5.85g boron oxide, 3.26g aluminum oxide, 1.12g calcium oxide, 0.21g sodium carbonate, 3.01g manganese bromide, 3.09g sodium bromide, and 0.27g stannous oxide. Add these to a 16cm diameter ceramic mortar and mix thoroughly. Place the resulting powder in a high-temperature muffle furnace preheated to 1300℃ and heat for 20 minutes to fully mix and react, obtaining a molten glass solution. Then, pour the molten glass solution onto a graphite mold preheated to 420℃ to cool and solidify, obtaining a glass precursor. Next, place the glass precursor in a low-temperature muffle furnace and heat it to 420℃, maintaining the temperature for 3 hours for annealing. Finally, cut the annealed glass to the required thickness. The glass was then polished sequentially on polishing machines with mesh sizes of 400, 800, 1200, 1500, 2000, 3000, 5000, and 8000 mesh, each polishing lasting 5 minutes. Afterward, the glass was transferred to a polishing machine fitted with a felt cloth, and diamond abrasive paste with mesh sizes of 8000, 15000, and 30000 mesh was applied to the felt cloth for polishing, each polishing lasting 10 minutes. Finally, the polished glass was placed in a low-temperature muffle furnace, heated to 550°C, and held for 20 hours for heat treatment to obtain a 7.0% concentration glass scintillator material with X-ray responsive properties, denoted as 7.0%MnBr2 or Al4B2O9:7.0%MnBr2.

[0053] Example 6

[0054] Weigh out 5.05g boron oxide, 3.02g aluminum oxide, 1.05g calcium oxide, 0.10g sodium carbonate, 3.01g manganese oxide, 1.21g sodium bromide, and 0.10g stannous oxide. Add these to a 16cm diameter ceramic mortar and mix thoroughly. Place the resulting powder in a high-temperature muffle furnace preheated to 1200℃ and heat for 10 minutes to fully mix and react, obtaining a molten glass solution. Then, pour the molten glass solution onto a graphite mold preheated to 400℃ to cool and solidify, obtaining a glass precursor. Finally, place the glass precursor in a low-temperature muffle furnace and heat it to 400℃, maintaining the temperature for 5 hours for annealing. The glass is then subjected to heat treatment; after annealing, it is cut to the required thickness and polished sequentially on polishing machines with grits of 400, 800, 1200, 1500, 2000, 3000, 5000, and 8000 mesh, each time for 5 minutes; then the glass is transferred to a polishing machine equipped with a cloth, and diamond abrasive paste of 8000, 15000, and 30000 mesh is applied to the cloth for polishing, each time for 10 minutes; finally, the polished glass is placed in a low-temperature muffle furnace, heated to 450°C, and held for 25 hours for heat treatment to obtain a glass scintillator material with X-ray responsive properties.

[0055] Example 7

[0056] Weigh out 7.00g boron oxide, 3.95g aluminum oxide, 1.50g calcium oxide, 0.40g sodium carbonate, 3.01g manganese chloride, 6.79g sodium bromide, and 0.51g stannous oxide. Add these to a 16cm diameter ceramic mortar and mix thoroughly. Place the resulting powder in a high-temperature muffle furnace preheated to 1300℃ and heat for 30 minutes to fully mix and react, obtaining a molten glass solution. Then, pour the molten glass solution onto a graphite mold preheated to 450℃ to cool and solidify, obtaining a glass precursor. Finally, place the glass precursor in a low-temperature muffle furnace and heat it to 450℃, maintaining the temperature for 2 hours for annealing. The glass is then subjected to heat treatment; after annealing, it is cut to the required thickness and polished sequentially on polishing machines with grits of 400, 800, 1200, 1500, 2000, 3000, 5000, and 8000 mesh, each time for 5 minutes; then the glass is transferred to a polishing machine equipped with a velvet cloth, and diamond abrasive paste of 8000, 15000, and 30000 mesh is applied to the velvet cloth for polishing, each time for 10 minutes; finally, the polished glass is placed in a low-temperature muffle furnace, heated to 650°C, and held for 5 hours for heat treatment to obtain a glass scintillator material with X-ray responsive properties.

[0057] Comparative Example 1

[0058] The only difference between this comparative example and Example 1 is that no manganese source was added, resulting in a glass scintillator material with X-ray responsive properties at a concentration of 0.0%, denoted as 0.0% MnBr2.

[0059] Experimental Example 1

[0060] The glass scintillator materials with X-ray response properties prepared in Comparative Example 1 and Examples 1-5 were subjected to X-ray diffraction (XRD) analysis. By observing the scattering and diffraction phenomena of X-rays with the crystalline phase atoms in the glass scintillator, and combining this with Bragg's law 2dsinθ=nλ, the composition and crystal structure of the glass scintillator materials were determined. Figure 1 As shown, from Figure 1 As can be seen, Comparative Example 1 did not exhibit crystallization characteristics due to the absence of a manganese source. However, as the concentration of manganese ions increased in Examples 1 to 5, the XRD peak values ​​became higher and higher, showing increasingly stronger crystallization characteristics. This indicates that the addition of a manganese source induces glass crystallization.

[0061] Experiment Example 2

[0062] The glass scintillator materials with X-ray responsive properties prepared in Examples 1-5 were irradiated under natural light, 375nm ultraviolet light, and X-rays, respectively; Figure 2As shown, from the tail of the arrow to the tip, they are the glass scintillator materials of Examples 1, 2, 3, 4, and 5, respectively. Figure 2 As can be seen, under natural light, the glass scintillator material prepared by this invention has high transparency, and the text behind the glass scintillator material can be clearly seen; under ultraviolet light, it can be seen that the glass scintillator material prepared by this invention can adjust the emission color of the glass scintillator material with the change of manganese ion concentration, proving that the glass scintillator material prepared by this invention has the characteristic of continuously adjustable emission; under X-rays, it can be seen that the glass scintillator material prepared by this invention has good emission uniformity, which is the primary prerequisite for the preparation of large-area glass scintillator materials.

[0063] Experimental Example 3

[0064] In this experiment, a fluorescence spectrometer (model FL3-21, manufactured by Horiba, Japan) was used to characterize the radiative luminescence properties of the glass scintillator materials. The glass scintillator materials with X-ray responsiveness prepared in Examples 1-5 were subjected to radiative luminescence (RL) spectroscopy. RL is the process by which electrons in a glass scintillator material, when excited by X-rays, transition from a low-energy ground state to a higher-energy excited state. Since electrons in the excited state are extremely unstable, they spontaneously transition back to the ground state and emit photons. For glass scintillator materials, stronger radiative luminescence is desirable. The test results are as follows: Figure 3 As shown, from Figure 3 As can be seen, the glass scintillator material prepared in Example 3 is the optimal material, possessing the strongest radiative luminescence capability.

[0065] Experiment Example 4

[0066] The glass scintillator material with X-ray responsive properties prepared in Example 3 was subjected to high-temperature imaging stability testing. The materials had an area of ​​12.56 cm². 2 The glass scintillator material was heated from 25°C to 100°C, 200°C, 300°C, 400°C, and 500°C, and then, under X-ray excitation, unidentified objects behind the glass scintillator material were detected and imaged; for example... Figure 4 As shown, from Figure 4 As can be seen, the area is 12.56 cm². 2 The glass scintillator material exhibits excellent detection and imaging performance at 400℃, clearly revealing rod-shaped objects and Chinese knots. When the temperature reaches 500℃, the clarity decreases due to red background interference caused by blackbody radiation, but it can still present a certain imaging effect. This demonstrates that the large-area glass scintillator material prepared by this invention has extremely strong stability and can cope with large-area X-ray detection and imaging under extreme environments.

[0067] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a glass scintillator material with X-ray responsive properties, characterized in that, Includes the following steps: (1) Mix boron oxide, aluminum oxide, calcium oxide, sodium carbonate, manganese source, sodium bromide and stannous oxide and react to obtain a molten glass solution; (2) Cool the molten glass solution on a preheated mold to obtain a glass precursor; (3) The glass precursor is annealed, polished and heat-treated in sequence to obtain a glass scintillator material with X-ray response performance; The glass scintillator material with X-ray responsive properties includes Al4B2O9 crystal material doped with MnBr2.

2. The method for preparing a glass scintillator material with X-ray responsive properties according to claim 1, characterized in that, In step (1), the mass ratio of boron oxide, aluminum oxide, calcium oxide, sodium carbonate, manganese source, sodium bromide and stannous oxide is 5~7:3~4:1.0~1.5:0.1~0.4:0.2~3:2~5:0.1~0.

5.

3. The method for preparing a glass scintillator material with X-ray responsive properties according to claim 2, characterized in that, The manganese source in step (1) includes one or more of manganese bromide, manganese chloride, and manganese oxide.

4. The method for preparing a glass scintillator material with X-ray responsive properties according to claim 3, characterized in that, The reaction temperature in step (1) is 1200~1400 ℃ and the reaction time is 10~30 minutes.

5. A method for preparing a glass scintillator material with X-ray responsive properties according to any one of claims 1 to 4, characterized in that, The temperature of the preheated mold in step (2) is 400~450 ℃.

6. The method for preparing a glass scintillator material with X-ray responsive properties according to claim 5, characterized in that, In step (3), the annealing temperature is 400~450 ℃ and the annealing time is 2~5 hours.

7. The method for preparing a glass scintillator material with X-ray responsive properties according to claim 6, characterized in that, The heat treatment temperature in step (3) is 450~650 ℃, and the heat treatment time is 5~25 hours.

8. The glass scintillator material with X-ray responsive properties prepared by the method for preparing a glass scintillator material with X-ray responsive properties according to any one of claims 1 to 7.

9. The application of the glass scintillator material with X-ray response properties as an X-ray detection material as described in claim 8.

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