Cerium / praseodymium co-doped high gadolinium boron aluminosilicate fluorine oxygen scintillation glass and preparation method and application thereof
By adding Pr3+ ions to cerium-doped high-gadolinium boroaluminosilicate fluorine scintillation glass and co-doping with Ce3+ ions, the problems of low luminous efficiency and long decay time of gadolinium-based scintillation glass are solved, achieving efficient energy transfer and fast decay scintillation performance, which is suitable for high-energy physics research and medical imaging.
Patent Information
- Application Number
- CN202510952023.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-10
- Publication Date
- 2025-11-14
AI Technical Summary
Existing gadolinium-based scintillation glasses have low luminous efficiency, long decay time, and imperfect energy transfer mechanisms, which limit their application in fields such as high-energy physics research and medical imaging.
By adding Pr3+ ions to cerium-doped high-gadolinium boroaluminosilicate fluorine scintillation glass and co-doping with Ce3+ ions, the efficient energy transfer between Pr and Ce can be utilized to improve luminescence intensity and shorten decay time.
It achieves high density, good chemical stability, high scintillation efficiency, and fast decay scintillation performance, improving the luminescence intensity and response speed of the material, making it suitable for matching with SiPM.
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Figure CN120943523A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of scintillation glass, and particularly relates to a cerium / praseodymium co-doped high gadolinium boroaluminosilicate fluorine scintillation glass, its preparation method and application. Background Technology
[0002] Scintillation materials are materials that convert high-energy particles (such as electrons, hadrons, and protons) and high-energy rays (such as X-rays and beta rays) into ultraviolet or visible light. Over the past few decades, the use of scintillation materials in high-energy physics experiments, security inspections, industrial non-destructive testing, geophysical exploration, radioactivity detection, and medical diagnostic imaging has seen tremendous growth.
[0003] With the development of various industries, the performance requirements for scintillation materials in applications are constantly increasing. These requirements include high density, high light yield, short fluorescence lifetime, and radiation resistance. Simultaneously, considering different application scenarios and cost issues, the development of novel scintillation materials must be prioritized. No single material is superior for all applications; in most cases, to find the ideal scintillation material, methods are often adopted to improve one or more properties of the scintillation material.
[0004] Currently, scintillation glass has advantages such as simple preparation process, easy adjustment of components, good matrix uniformity, isotropy, convenient processing, low cost, and easy realization of mass production and large-size industrial production, making it a very promising scintillation material.
[0005] Gadolinium-based scintillation glasses have gradually become a research hotspot due to their high density, excellent luminescent properties, and good thermal stability. Gadolinium (Gd) is a rare earth element, and its oxidation state is Gd. 3 Rare earth elements (+) possess high atomic numbers and low atomic weights, giving them excellent X-ray absorption and radiation detection sensitivity in scintillation glasses. However, single rare earth ions (such as Gd)... 3 +) Doped scintillation glasses typically have long decay times (on the order of milliseconds), short emission wavelengths (312 nm), and are outside the sensitive detection range of detectors, making them difficult to apply. Furthermore, they may undergo phase separation or crystallization at high temperatures, affecting the material's stability and lifespan, thus limiting their application areas.
[0006] Among rare earth elements, Ce 3+ Ions possess a broad absorption band and low excitation energy, enabling them to effectively capture high-energy radiation and generate strong blue light emission, thereby improving the luminescence intensity and response speed of scintillation glass. They have been used to develop high-efficiency scintillation glass materials. 3+Ion-activated high-gadolinium boroaluminosilicate fluorine-oxygen scintillation exhibits advantages such as high luminous intensity, high light yield, short fluorescence lifetime, ultrafast scintillation decay time, chemical stability, and good transmittance. Its emission peak is located near 420 nm, making it well-matched with silicon photomultiplier tubes (SiPMs). It shows great promise for applications in high-energy physics research, X-ray medical imaging, and metal flaw detection. Meanwhile, Pr... 3+ Ions exhibit two types of luminescence; their df transition has high luminescence efficiency, but it is similar to Gd... 3+ Similarly, its emission wavelength is too short; and its ff transition scintillation lifetime is too long, making it unsuitable for fast scintillation detection. Therefore, by co-doping cerium and praseodymium, the luminous efficiency, thermal stability, and radiation detection capability of gadolinium-based scintillation glasses can be greatly improved by utilizing their df transition and Pr-Ce energy exchange.
[0007] To date, no one has attempted to use Pr. 3+ Ions are used to improve the scintillation efficiency of cerium-doped high-gadolinium boroaluminosilicate fluorine scintillation glass. Summary of the Invention
[0008] To overcome the problems of low luminous efficiency, long decay time, and imperfect energy transfer mechanism in existing gadolinium-based scintillation glasses, this invention proposes a cerium / praseodymium-doped high-gadolinium boroaluminosilicate fluorine-oxygen scintillation method and its preparation method, utilizing Pr 3+ With Ce 3 + The efficient energy transfer between components enhances the scintillation performance and stability of the material, while simultaneously achieving synergistic optimization of high density, fast decay, and high light yield. It possesses advantages such as high density, good chemical stability, high scintillation efficiency, high photoluminescence intensity, and fast scintillation decay.
[0009] The present invention proposes a cerium / praseodymium-doped high gadolinium boroaluminosilicate fluorine-oxygen scintillation method, wherein the doping composition comprises, by molar percentage: CeO2: 1-10%, Pr2O3: 0-0.5%;
[0010] Preferably, the molar ratio of cerium oxide (CeO2) to praseodymium oxide (Pr2O3) is 1:0.01 to 0.5;
[0011] Preferably, the composition of the scintillation glass comprises, by molar percentage: SiO2: 18.0%, B2O3: 27.0%, Al2O3: 12.0%, Gd2O3: 18.0%, GdF3: 24.0%, CeO2: 1.0%, and Pr2O3: 0.05%.
[0012] Preferably, the density of the scintillating glass is 5.0-6.0 g / cm³. 3 .
[0013] This invention proposes a method for preparing cerium / praseodymium-doped gadolinium-based borosilicate scintillation glass, comprising:
[0014] (1) SiO2, H3BO3, Al2O3, Gd2O3, GdF3, CeO2 and Pr2O3 are used as raw materials and weighed according to the composition. They are then ground and mixed to obtain glass feedstock.
[0015] (2) The glass ingredients are placed in a crucible and melted in a reducing atmosphere at a melting temperature of 1300-1400℃. The melting temperature is maintained for 0.5-2 hours to obtain glass melt. The reducing atmosphere is achieved by the crucible nesting method, which is to place the crucible containing the raw materials into a large crucible containing graphite powder and then cover it with a lid.
[0016] (3) The glass melt is cast into a mold and then annealed to obtain the scintillation glass.
[0017] Preferably, the annealing temperature is 450-550℃ and the time is 4-8h.
[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0019] Adding Pr₂O₃ to cerium-doped gadolinium-based borosilicate scintillation glass improves the energy transfer efficiency between Pr and Ce, thereby enhancing Ce's performance. 3+ The luminous intensity; on the other hand, Pr 3+ This can shorten the decay time of fast components, resulting in faster scintillation decay time for cerium-doped gadolinium boroaluminosilicate fluorine-oxygen scintillation. Attached Figure Description
[0020] Figure 1 The emission spectra of the scintillation glass X-ray excitation described in Example 2 and Comparative Example 1 are shown.
[0021] Figure 2 The emission spectra of the scintillation glass described in Example 2 and Comparative Example 1 under 275 nm excitation are shown. Detailed Implementation
[0022] The technical solution of the present invention will now be described in detail through specific embodiments.
[0023] In the cerium / praseodymium-doped high-gadolinium boroaluminosilicate fluorine-oxygen scintillation process described in this invention, Ce... 3+ and Pr 3+ A rare-earth ion-doped high-gadolinium boroaluminosilicate fluorine-oxygen scintillation glass was prepared using rare-earth ion doping as the main doping ion. The scintillation glass was prepared by a high-temperature melting process.
[0024] The scintillation glass comprises a glass matrix and luminescent centers. The glass matrix is borosilicate glass mainly doped with Al2O3, Gd2O3, and GdF3, and the luminescent centers are Pr 3+ / Ce 3+ Co-doped ions.
[0025] In the glass matrix, Al₂O₃ acts as a network intermediate, enhancing the network strength, stabilizing the glass structure, and improving its resistance to crystallization. Furthermore, the introduction of Al₂O₃ increases the melt viscosity of the glass and has a certain moderating effect on its coefficient of thermal expansion. SiO₂, as the primary network former, constructs a three-dimensional network structure through Si-O bonds, endowing the glass with excellent mechanical strength and chemical stability. B₂O₃ can act as both a network former, forming local network structures through BO bonds, and an intermediate, connecting different network structures. Moreover, the introduction of B₂O₃ can significantly lower the melting temperature of the glass, increase its formability, and expand the glass formation area. Gd₂O₃, as the main host material, can effectively capture high-energy radiation and convert it into visible or near-infrared light, while providing a suitable crystal field environment to maximize the luminous efficiency of the luminescent centers. GdF₃, through the introduction of F… - Lowering the melting temperature of the glass and regulating the composite light emission process further optimizes the scintillation performance.
[0026] In the luminescent center, Pr is uniformly distributed 3+ Ions can efficiently transfer energy to Ce. 3+ Ion luminescent centers further optimize scintillation performance through synergistic effects and energy transfer mechanisms, improving luminescence efficiency while effectively reducing fluorescence lifetime.
[0027] The following is an exemplary description of the preparation method of cerium / praseodymium-doped high-gadolinium boroaluminosilicate fluorine scintillation provided by the present invention.
[0028] According to the composition of the scintillation glass, weigh out SiO2 raw materials, B2O3 raw materials, Al2O3 raw materials, Gd2O3 raw materials, GdF3 raw materials, CeO2 raw materials and Pr2O3 raw materials, and mix them evenly to obtain the glass feedstock; among which, the B2O3 raw material is H3BO3.
[0029] The glass ingredients are melted at 1300-1400℃ and held at that temperature for 0.5-2 hours to obtain a glass melt. The glass melt is then poured into a mold and pressed into glass. The obtained glass is then annealed to eliminate internal stress. The annealing temperature can be 450-550℃ and the annealing time can be 4-8 hours. Large pieces of shimmering glass are then cast.
[0030] The scintillation glass obtained above is processed into the scintillation glass described in this invention after cutting, surface grinding and polishing.
[0031] Examples 1-10
[0032] The scintillation glass in this embodiment can be prepared in the following manner:
[0033] Referring to the glass composition in Table 1 below, use an electronic balance (accurate to 0.01g) to accurately weigh SiO2 raw materials, B2O3 raw materials, Al2O3 raw materials, Gd2O3 raw materials, GdF3 raw materials, CeO2 raw materials and Pr2O3 raw materials, and prepare a total of 100g of materials. Then use an agate mortar to grind and mix them thoroughly.
[0034] Table 1. Composition of the scintillation glass in Examples 1-10
[0035]
[0036]
[0037] The mixture is then added to a crucible, and the crucible containing the raw materials is placed into a large crucible containing graphite powder. The lid is then placed on the crucible and melted in an electric furnace. The temperature is raised from room temperature to 1350°C over 6 hours and held at 1350°C for 30 minutes. The molten glass from the crucible taken out of the high-temperature furnace is then poured into a mold. The mold is then placed in a muffle furnace at 550°C for annealing for 6 hours, and then cooled to room temperature along with the furnace.
[0038] The obtained glass sample was ground into a 5mm thick sheet using a grinding machine, and then polished to obtain a 5×5×5mm sheet. 3 Standardized scintillation glass samples were then subjected to performance testing.
[0039] Comparative Example 1
[0040] This comparative example scintillation glass is a Ce-doped high-gadolinium boroaluminosilicate fluorine scintillation glass without Pr doping, which can be prepared in the following manner:
[0041] Referring to the glass composition in Table 2 below, use an electronic balance (accurate to 0.01g) to accurately weigh SiO2 raw materials, B2O3 raw materials, Al2O3 raw materials, Gd2O3 raw materials, GdF3 raw materials, CeO2 raw materials and Pr2O3 raw materials, and prepare a total of 100g of materials. Then use an agate mortar to grind and mix them thoroughly.
[0042] Table 2. Composition of the scintillation glass in Comparative Example 1
[0043]
[0044] The mixture is then added to a crucible, which is then placed into a large crucible containing graphite powder. The lid is then placed on the crucible and melted in an electric furnace. The temperature is raised from room temperature to 1300°C over 6 hours and held at that temperature for 30 minutes. The molten glass from the crucible taken out of the high-temperature furnace is then poured into a mold. The mold is then placed in a muffle furnace at 500°C for annealing for 4 hours, and then cooled to room temperature along with the furnace.
[0045] The obtained glass sample was ground into a 5mm thick sheet using a grinding machine, and then polished to obtain a 5×5×5mm sheet. 3 Standardized scintillation glass samples were then subjected to performance testing.
[0046] The performance of the samples described in Examples 1-5 and Comparative Example 1 was studied. The scintillation intensity was calibrated using the luminescence intensity of the BGO scintillation crystal as 100%; the photoluminescence intensity was calibrated using the luminescence intensity of Comparative Example 1 as 100%.
[0047] The results are shown in Table 3 below:
[0048]
[0049] As can be seen from the above performance measurement results, the scintillation glass of the present invention has a large density and a strong ability to stop detected particles. It emits obvious blue light (main wavelength 380nm) under laser light source irradiation. Furthermore, at 380nm, the luminous intensity of the scintillation glass described in the embodiment is more than 1.5 times that of the comparative sample.
[0050] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.
Claims
1. A cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass, characterized in that, The composition of the scintillating glass by molar percentage includes: SiO2: 16.8–18.0%, B2O3: 25.1–27.0%, Al2O3: 11.2–12.0%, Gd2O3: 16.8–18.0%, GdF3: 22.3–24.0%, CeO2: 1.0–10%, and Pr2O3: 0.01–0.5%, wherein the molar ratio of CeO2 to Pr2O3 is 1:0.01–0.
5.
2. The cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass according to claim 1, characterized in that, The molar percentage of CeO2 is 1.0–7.4%, and the molar percentage of Pr2O3 is 0.01–0.4%.
3. The cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass according to claim 1, characterized in that, The molar percentage of CeO2 is 1.0%, and the molar ratio of Pr2O3 is 0.
05.
4. The cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass according to any one of claims 1-3, characterized in that, The density of the scintillating glass is 5.0-6.0 g / cm³. 3 .
5. The cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass according to claim 4, characterized in that, The refractive index of the scintillating glass is 1.65 to 1.
75.
6. The cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass according to any one of claims 1-3, characterized in that, The light yield of the scintillation glass under X-ray excitation is 19-45% of that of the BGO crystal.
7. The cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass according to any one of claims 1-3, characterized in that, The fast flicker decay time of the scintillating glass is 68.9–91.3 ns, and the slow flicker decay time is 736.9–1988.3 ns.
8. A method for preparing a cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass according to any one of claims 1-4, characterized in that, Includes the following steps: (1) SiO2, H3BO3, Al2O3, Gd2O3, GdF3, CeO2 and Pr2O3 are used as raw materials and weighed according to the composition. They are then ground and mixed to obtain glass feedstock. (2) The glass ingredients are melted at 1300-1400℃ for 0.5-2 hours to form a homogeneous glass melt; (3) The glass melt is poured into a mold and annealed at 450-550℃ for 4-8 hours to obtain the scintillation glass.
9. The method for preparing cerium / praseodymium co-doped high-gadolinium boroaluminosilicate fluorine scintillation glass according to claim 8, characterized in that, The melting temperature is 1350℃, preferably 1350℃, and the holding time is 0.5h.
10. A scintillation detector, characterized in that, The scintillator material includes the cerium / praseodymium co-doped high gadolinium boroaluminosilicate fluorine scintillation glass as described in any one of claims 1 to 7.
11. The scintillation detector according to claim 9, characterized in that, The detector is selected from X-ray CT detectors, PET detectors, gamma-ray detectors, or high-energy particle detectors.