Rare earth metal halide glass scintillator material with thermal quenching resistance as well as preparation method and application of rare earth metal halide glass scintillator material
By preparing rare-earth metal halide glass scintillator materials with anti-thermal quenching properties, the problems of thermal quenching of crystal scintillators at high temperatures and low light yield of glass scintillators have been solved, achieving stable X-ray detection performance at high temperatures and expanding the application range.
Patent Information
- Application Number
- CN202511080892.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-31
- Publication Date
- 2025-11-21
AI Technical Summary
Existing crystal scintillators face problems such as severe thermal quenching, moisture absorption, and complicated preparation processes at high temperatures. Furthermore, glass scintillators exhibit significant non-radiative relaxation at high temperatures, resulting in low light yield and making it difficult to meet the requirements of high-performance X-ray detection.
By mixing boron oxide, aluminum oxide, lithium carbonate, terbium fluoride, sodium fluoride, and gadolinium fluoride, melting them at high temperature, and then cooling them, followed by annealing, polishing, and heat treatment, nanocrystals are precipitated, thereby altering the internal defect structure of the glass and preparing a rare earth metal halide glass scintillator material with anti-thermal quenching properties.
This achievement improves the anti-thermal quenching performance at high temperatures, increases light yield, enhances material stability, and enables long-term stable operation in high-temperature environments, thus expanding the application fields of X-ray detection materials.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of glass scintillator materials, and particularly relates to a rare earth metal halide glass scintillator material with anti-thermal quenching performance and a preparation method and application thereof. BACKGROUND
[0002] At present, the crystal scintillators (such as NaI:Tl, Cs2LiYCl6:Ce, GSO:Ce, etc.) serving in high-temperature environments face serious thermal quenching phenomenon when facing high-temperature scenes such as deep environment and nuclear facilities, and the light output loss is large, thereby affecting the stable X-ray detection performance. At the same time, the crystal is hygroscopic and corroded, and needs to be packaged, and the cost is high. Therefore, the research and development of a new generation of high-temperature scintillator materials is increasingly important.
[0003] Glass scintillators have thermal stability, non-hygroscopicity, corrosion resistance and simple preparation process due to their dense amorphous network structure, which makes them have strong competitiveness compared with traditional crystal scintillators. However, glass scintillators still face the problem of a large number of defects in the glass matrix, which leads to strong non-radiative relaxation and reduces the light yield. This hinders the further development of glass scintillators. At present, the method for improving the light yield of glass scintillators at room temperature mainly reduces defects through microcrystallization. The ordered structure of the crystal can effectively reduce non-radiative relaxation. However, at high temperatures, molecular or ionic vibration will be enhanced, and the probability of non-radiative relaxation will increase sharply. Therefore, simply reducing defects cannot improve the high-temperature performance of glass scintillators. Under X-ray excitation, a large number of electrons and holes (carriers) are generated, and the defect structure in the glass can store the carriers, which will be released at high temperatures to make up for the light loss caused by thermal quenching, so that the glass scintillator has the potential to be applied in high-temperature environments. However, how to utilize and design the defects of glass scintillators still needs to solve the following problems: 1) Due to a large number of defect structures, glass scintillators have more non-radiative relaxation, which leads to low light yield and is difficult to meet the demand of high-performance X-ray detection; 2) There is a problem of defect depth selection. Shallow defects cannot be used as carrier storage medium, while deep defects make it difficult for carriers to be released, and the light yield further decreases, making it difficult to realize anti-thermal quenching at high temperatures.
[0004] Therefore, it is of great significance to provide a scintillation glass material with anti-thermal quenching performance at high temperatures and a simple process. SUMMARY
[0005] The present application aims to provide a rare earth metal halide glass scintillator material with anti-thermal quenching performance and a preparation method and application thereof, so as to solve the technical problems of serious thermal quenching of existing crystal scintillators in high-temperature environments, hygroscopicity of crystal scintillators and complicated preparation process.
[0006] In order to achieve the above-mentioned purposes of the application, the application provides the following technical solutions.
[0007] The application provides a preparation method of a rare earth metal halide glass scintillator material with anti-thermal quenching performance.
[0008] 1) mixing boron oxide, aluminum oxide, lithium carbonate, terbium fluoride, sodium fluoride and gadolinium fluoride, and then performing reaction to obtain a molten glass solution;
[0009] 2) cooling the molten glass solution to obtain a glass precursor;
[0010] 3) sequentially performing annealing, polishing and heat treatment on the glass precursor to obtain the glass scintillator material with anti-thermal quenching performance.
[0011] Further, in the step 1), the mass ratio of the boron oxide, the aluminum oxide and the lithium carbonate is 3-4:1-2:0.3-0.4;
[0012] The mass ratio of the boron oxide, the terbium fluoride, the sodium fluoride and the gadolinium fluoride is 3-4:2.2-3:0.5-0.6:2-3.
[0013] Further, in the step 1), the reaction temperature is 1200-1400 DEG C, and the reaction time is 10-30 min.
[0014] Further, in the step 2), the cooling temperature is 450-500 DEG C.
[0015] Further, in the step 3), the annealing temperature is 450-500 DEG C, and the annealing time is 2-5 h.
[0016] Further, in the step 3), the heat treatment temperature is 500-550 DEG C, and the heat treatment time is 3-10 h.
[0017] The application provides a rare earth metal halide glass scintillator material with anti-thermal quenching performance.
[0018] The application also provides an application of the rare earth metal halide glass scintillator material with anti-thermal quenching performance in an X-ray detection material.
[0019] The application has the following beneficial effects:
[0020] 1) The application uses Tb as a light emitting center, successfully precipitates nanocrystals through a high-temperature melting quenching method and a subsequent heat treatment process, changes the defect structure distribution in the glass, realizes the anti-thermal quenching performance under high-temperature conditions, and has a large area; the preparation method of the application is simple, short in time, and controllable in thickness size, and significantly promotes the industrialized production of large-area high-temperature X-ray detection materials;
[0021] 2) The preparation method of the present application can prepare X-ray detection materials with a detection limit lower than 2.73 muGy / s, a light yield higher than 6000 photons / MeV, and a resolution not lower than 20 lp / mm. Compared with existing glass scintillators, the X-ray detection materials have better anti-thermal quenching performance at high temperatures, and the glass scintillator materials prepared by the preparation method have an area of up to 100 cm 2 , strong stability, which enables long-term stable operation in a high-temperature environment, thereby expanding the application field of X-ray detection materials;
[0022] 3) The preparation method of the present application can realize anti-thermal quenching in a temperature range of 25-400 DEG C, and has extremely stable high-temperature imaging performance. BRIEF DESCRIPTION OF DRAWINGS
[0023] Figure 1 Radiation luminescence diagram of the glass scintillator materials prepared for Examples 1-2 and Comparative Examples 1-4;
[0024] Figure 2 XRD diagram of the glass scintillator materials prepared for Example 1 and Comparative Example 5;
[0025] Figure 3 Radiation luminescence diagram of the glass scintillator materials prepared for Example 1 at different temperatures;
[0026] Figure 4 High-temperature imaging diagram of the glass scintillator materials prepared for Example 1. DETAILED DESCRIPTION
[0027] The present application provides a preparation method of a rare earth metal halide glass scintillator material with anti-thermal quenching performance, comprising the following steps:
[0028] 1) Mixing boron oxide, aluminum oxide, lithium carbonate, terbium fluoride, sodium fluoride and gadolinium fluoride, and then reacting to obtain a molten glass solution;
[0029] 2) Cooling the molten glass solution to obtain a glass precursor;
[0030] 3) Sequentially annealing, polishing and heat-treating the glass precursor to obtain a glass scintillator material with anti-thermal quenching performance.
[0031] In the present application, in the step 1), the mass ratio of the boron oxide, the aluminum oxide and the lithium carbonate in the step 1) is 3-4:1-2:0.3-0.4, preferably 3.3-3.5:1.5-1.9:0.35-0.39, and further preferably 3.48:1.78:0.38;
[0032] The mass ratio of the boron oxide, terbium fluoride, sodium fluoride and gadolinium fluoride is 3-4:2.2-3:0.5-0.6:2-3, preferably 3.3-3.5:2.2-2.9:0.5-0.55:2.5-2.9, and further preferably 3.48:2.26-2.82:0.54:2.74.
[0033] In the present application, in the step 1), the reaction temperature is 1200-1400℃, preferably 1200-1300℃, and further preferably 1200℃; and the reaction time is 10-30min, preferably 15-25min, and further preferably 20min.
[0034] In the present application, in the step 2), the cooling temperature is 450-500℃, preferably 460-490℃, and further preferably 470-480℃.
[0035] In the present application, the cooling is performed in a preheated mold, and the preheated mold includes a copper mold or a graphite mold.
[0036] In the present application, in the step 3), the annealing temperature is 450-500℃, preferably 450-490℃, and further preferably 450-480℃; and the annealing time is 2-5h, preferably 2.5-4.5h, and further preferably 3-4h.
[0037] In the present application, the purpose of the annealing is to eliminate the internal stress of the glass and prevent cracking.
[0038] In the present application, after the annealing, the glass precursor is further cut into a desired shape and thickness.
[0039] In the present application, the polishing operation is as follows: the cut glass precursor is fixed on a polishing machine provided with sandpaper of different mesh numbers, and polished for 5min for each mesh number, and then the polished glass is transferred to a polishing machine provided with a velvet cloth, and polished for 10min for each mesh number on the velvet cloth coated with diamond abrasive paste of different mesh numbers, to obtain a transparent glass precursor.
[0040] In the present application, the mesh number of the sandpaper is 400-2000, preferably 400, 800, 1200, 1500 or 2000;
[0041] The different mesh numbers of the diamond abrasive paste are 2000-8000, preferably 2000, 5000 or 8000.
[0042] In the present application, in the step 3), the temperature of the heat treatment is 500-550 DEG C, preferably 510-540 DEG C, further preferably 520-530 DEG C; the time of the heat treatment is 3-10 h, preferably 4-9 h, further preferably 5-8 h.
[0043] In the present application, the purpose of the heat treatment is to change the internal defects of the glass sufficiently.
[0044] The present application provides a rare earth metal halide glass scintillator material with anti-thermal quenching performance.
[0045] The present application also provides an application of the rare earth metal halide glass scintillator material with anti-thermal quenching performance in X-ray detection material.
[0046] The technical solutions provided by the present application will be described in detail below in combination with embodiments, but they should not be understood as limiting the protection scope of the present application.
[0047] Example 1
[0048] 3.48g of boron oxide, 1.78g of aluminum oxide, 0.38g of lithium carbonate, 2.26g of terbium fluoride, 0.54g of sodium fluoride and 2.74g of gadolinium fluoride are added into a ceramic mortar with a diameter of 16cm, and after being mixed uniformly, they are put into a high-temperature muffle furnace preheated to 1200 DEG C to react, the reaction time is 20min, and a molten glass solution is obtained; then the molten glass solution is poured on a graphite mold preheated to 450 DEG C to cool, and a glass precursor is obtained; then the glass precursor is put into a low-temperature muffle furnace, and the furnace is heated to 450 DEG C, and annealed for 3 hours; then the annealed glass is cut into the required thickness, and is polished on a polishing machine with a mesh of 400, 800, 1200, 1500 and 2000, respectively, and each time for 5min; then the glass is transferred to a polishing machine with a polishing cloth, and is polished on the polishing cloth with diamond abrasive paste with a mesh of 3000, 5000 and 8000, respectively, and each time for 10min; finally, the polished glass is put into a low-temperature muffle furnace, and the furnace is heated to 530 DEG C, and heat-treated for 3 hours, and a glass scintillator material with anti-thermal quenching performance containing nanocrystalline phase is obtained, and is recorded as Al4B2O9:8%Tb 3+ .
[0049] Example 2
[0050] Compared with example 1, the only difference is that in example 2, the mass of terbium fluoride is 2.82g, and is recorded as Al4B2O9:10%Tb 3+ .
[0051] Example 3
[0052] The difference between Example 1 and Example 3 is that the temperature of the reaction in Example 3 is 1400℃.
[0053] Example 4
[0054] The difference between Example 1 and Example 4 is that the temperature of the annealing in Example 4 is 500℃, and the time of the annealing is 2.5h.
[0055] Example 5
[0056] The difference between Example 1 and Example 5 is that the temperature of the heat treatment in Example 5 is 550℃, and the time of the heat treatment is 3h.
[0057] Comparative Example 1
[0058] The difference between Example 1 and Comparative Example 1 is only that the mass of terbium fluoride in Comparative Example 1 is 0.56g, which is recorded as Al4B2O9: 2% Tb 3+ .
[0059] Comparative Example 2
[0060] The difference between Example 1 and Comparative Example 2 is only that the mass of terbium fluoride in Comparative Example 2 is 1.13g, which is recorded as Al4B2O9: 4% Tb 3+ .
[0061] Comparative Example 3
[0062] The difference between Example 1 and Comparative Example 3 is only that the mass of terbium fluoride in Comparative Example 3 is 1.70g, which is recorded as Al4B2O9: 6% Tb 3+ .
[0063] Comparative Example 4
[0064] The difference between Example 1 and Comparative Example 4 is only that the mass of terbium fluoride in Comparative Example 4 is 3.39g, which is recorded as Al4B2O9: 12% Tb 3+ .
[0065] The performance of the glass scintillator materials prepared in Examples 1-2 and Comparative Examples 1-4 is tested, and the testing method is as follows: a fluorescence spectrometer produced by Japan Horiba Company with a model number of FL3-21 is used to characterize the radiation luminescence performance of the glass scintillator materials; the glass scintillator materials prepared in Examples 1-2 and Comparative Examples 1-4 are subjected to radiation luminescence spectrum analysis, that is, the process in which, under X-ray irradiation, electrons jump from a low-energy level ground state to a higher-energy level excited state, and the excited state electrons spontaneously jump to the ground state and radiate photons outward; for the glass scintillator materials, stronger radiation luminescence means better performance; the test results are shown in Table 1. Figure 1
[0066] Figure 1 It can be seen that the radiation luminous intensity increases with the concentration first, and then decreases due to concentration quenching, and finally the glass scintillator prepared in Example 1 is screened out with the strongest radiation luminous intensity, which is the best doping concentration.
[0067] Comparative Example 5
[0068] Compared with Example 1, the only difference is that no heat treatment is performed in Comparative Example 5, which is recorded as precursor glass.
[0069] The glass scintillator material with anti-thermal quenching performance prepared in Example 1 and Comparative Example 5 is subjected to X-ray diffraction analysis. Through the scattering and diffraction phenomenon of X-rays with the crystal phase atoms in the glass scintillator, combined with Bragg formula 2dsinθ=nλ, the composition and crystal structure of the glass scintillator material are judged. The test is as shown in Figure 2 .
[0070] From Figure 2 it can be seen that Comparative Example 5 does not show crystalline characteristics due to no heat treatment, while Example 1 shows crystalline characteristics after heat treatment.
[0071] The glass scintillator material with anti-thermal quenching performance prepared in Example 1 is subjected to high-temperature radiation luminous spectrum analysis, and the radiation luminous intensity at 25℃, 100℃, 200℃, 300℃ and 400℃ is tested respectively. The integral area is calculated and a line graph of intensity change with temperature is drawn. The test is as shown in Figure 3 .
[0072] From Figure 3 it can be seen that the radiation intensity of the glass scintillator material of Example 1 increases with the temperature in the range of 25-400℃ under X-ray excitation, showing anti-thermal quenching phenomenon. It shows that the glass scintillator material prepared in Example 1 has more excellent performance at high temperature.
[0073] The glass scintillator material with anti-thermal quenching performance prepared in Example 1 is subjected to high-temperature imaging stability test. The glass scintillator material with an area of 12.57cm 2 is heated from 25℃ to 100℃, 200℃, 300℃, 400℃ and 500℃ respectively, and the unknown object behind the glass scintillator material is detected and imaged under X-ray excitation; the test is as shown in Figure 4 .
[0074] From Figure 4 it can be seen that the glass scintillator material with an area of 12.57cm 2The glass scintillator luminescence of the application is enhanced with temperature, has excellent high-temperature detection performance, can clearly present the imaged object, and has a good imaging effect at 500 DEG C due to the red light interference of strong blackbody radiation, which shows that the prepared anti-thermal quenching glass scintillator material has strong high-temperature stability and can meet the stable X-ray detection imaging under extreme high-temperature environment.
[0075] From the above embodiments, the application provides a rare earth metal halide glass scintillator material with anti-thermal quenching performance, a preparation method and application thereof, which comprises the following steps: uniformly mixing boron oxide, aluminum oxide, lithium carbonate, terbium fluoride, sodium fluoride and gadolinium fluoride, then high-temperature melting, then cooling, and finally annealing, polishing and heat treatment to obtain the glass scintillator material with anti-thermal quenching performance. The preparation method of the application controls the glass defect structure by precipitating nanocrystals, and prepares the glass scintillator material with anti-thermal quenching, large area, super stability and excellent performance, so that the glass scintillator material can serve for a long time under high-temperature environment, and the application range of the glass scintillator material is expanded.
[0076] The above only describes the preferred embodiments of the application, and it should be pointed out that, for ordinary skilled in the art, some improvements and refinements can be made without departing from the principles of the application, and these improvements and refinements should also be considered as the protection scope of the application.
Claims
1. A method of producing a rare earth metal halide glass scintillator material having anti-thermal quenching properties, characterized by, The method comprises the following steps: 1) mixing boron oxide, aluminum oxide, lithium carbonate, terbium fluoride, sodium fluoride and gadolinium fluoride, and then reacting to obtain a molten glass solution; 2) cooling the molten glass solution to obtain a glass precursor; 3) sequentially annealing, polishing and heat treating the glass precursor to obtain a rare earth metal halide glass scintillator material with anti-thermal quenching performance.
2. The method of making a rare earth halide glass scintillator material with anti-thermal quenching properties according to claim 1, wherein, In the step 1), the mass ratio of the boron oxide, aluminum oxide and lithium carbonate is 3-4:1-2:0.3-0.4; The mass ratio of the boron oxide, terbium fluoride, sodium fluoride and gadolinium fluoride is 3-4:2.2-3:0.5-0.6:2-3.
3. The method of producing a rare earth metal halide glass scintillator material having an anti-thermal quenching property according to claim 1 or 2, characterized in that, In the step 1), the reaction temperature is 1200-1400 ℃, and the reaction time is 10-30 min.
4. The method of making a rare earth halide glass scintillator material with anti-thermal quenching properties according to claim 3, wherein, In the step 2), the cooling temperature is 450-500 ℃.
5. The method of making a rare earth halide glass scintillator material with anti-thermal quenching properties according to claim 4, wherein, In the step 3), the annealing temperature is 450-500 ℃, and the annealing time is 2-5 h.
6. The method of making a rare earth halide glass scintillator material with anti-thermal quenching properties according to claim 5, wherein, In the step 3), the heat treatment temperature is 500-550 ℃, and the heat treatment time is 3-10 h.
7. A rare earth metal halide glass scintillator material with anti-thermal quenching performance, which is prepared by the preparation method of any one of claims 1-6.
8. Application of the rare earth metal halide glass scintillator material with anti-thermal quenching performance of claim 7 in X-ray detection materials.