Gadolinium aluminum borosilicate oxyfluoride scintillation glass and preparation method therefor

Abstract

Colorless and transparent gadolinium aluminum borosilicate oxyfluoride scintillation glass and a preparation method therefor. The gadolinium aluminum borosilicate oxyfluoride scintillation glass comprises: 16-61.5 mol% of Gd2O3, 0-35 mol% of GdF3, 1-10 mol% of Al2O3, 15-40 mol% of B2O3, 5-20 mol% of SiO2, and 0.075-6.0 mol% of a luminescent center compound. By partially replacing gadolinium oxide with gadolinium fluoride, the melting temperature of the glass can be reduced, and the degree of erosion of molten glass to a crucible is reduced, thereby increasing the density of the glass to 6.0 g / cm3 or more. Furthermore, by changing the activation concentration of the luminescent center compound, the scintillation and time performance of the glass are improved. While maintaining high density, the scintillation glass can achieve a light yield exceeding 1000 ph / MeV, with a fast decay component of less than 100 ns.

Description

Gadolinium aluminum borosilicate oxyfluoride scintillating glass and preparation method thereof

[0001] Cross-references

[0002] This disclosure claims priority to Chinese patent application No. 202311742885.8, filed on December 18, 2023, entitled “Gadolinium Aluminum Borosilicate Scintillating Glass and Preparation Method Thereof,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to the technical field of scintillating materials, and in particular to a colorless and transparent gadolinium aluminum borosilicate oxyfluoride scintillating glass and a preparation method thereof. Background Art

[0004] Scintillator detectors, one of the most important radiation detectors, are commonly used in high-energy physics experiments, nuclear radiation detection, nuclear medicine, and industrial flaw detection. Scintillating materials can convert high-energy particles or radiation into visible light and are considered optically functional materials. Generally, solid scintillating materials can be divided into scintillating crystals, scintillating ceramics, plastic scintillators, and scintillating glass. Scintillating crystals offer excellent performance, but their growth process is complex and costly. Plastic scintillators have extremely fast decay times and stable performance, but they have low density and poor radiation resistance. Scintillating ceramics offer excellent physical and chemical stability and good scintillation performance. However, due to the large number of pores within them, achieving high transparency is difficult and the production cost is high. Therefore, glass scintillators, which offer high density, high transparency, and stable physical and chemical properties, are gaining increasing attention. Furthermore, glass is inexpensive and easy to mass-produce, making it a promising alternative to scintillating crystals in applications such as high-energy physics, and possesses broad application prospects.

[0005] With the rapid development of high-energy physics, the demand for scintillating materials is increasing, necessitating further research into these materials. The Chinese particle physics community has proposed building a circular electron-positron collider (CEPC). To accurately measure the properties of Higgs, W, and bosons, the CEPC requires a wide solid angle coverage, excellent particle discrimination, precise measurement of particle energy-momentum, high-precision collision vertex resolution, jet resolution, and flavor signatures. The CEPC's hadron calorimeter system requires a suitable scintillating material. Scintillating glass, with its advantages of simple preparation, low cost, and continuously tunable composition, is a top candidate for hadron calorimeters. However, hadron calorimeters require scintillating glass with high density, substantial light yield, fast decay time, and strong radiation resistance. Furthermore, the Compact Muon Solenoid (CMS) of the Large Hadron Collider (LHC) at CERN, Europe's largest collider, is also considering using scintillating glass as an alternative to existing designs. Furthermore, the Large Electron-Ion Collider (EIC) in the United States is also considering developing scintillating glass calorimeter technology. It can be seen from this that scintillating glass is likely to be the most important scintillator in the next generation of high-energy physics experiments.

[0006] High density is an important indicator of scintillating materials in high-energy physics experiments. High-density scintillators have a shorter radiation length, better stopping power against high-energy particles, and can improve the energy resolution of detectors while facilitating the compact design of large scientific equipment. Currently reported scintillating glass densities rarely exceed 6 g / cm. 3 , and high-density glass without exception contains heavy metal oxides such as PbO, Bi2O3, and Lu2O3. For example, Chinese patent publication CN1087066A discloses a method for preparing scintillating glass with PbO and Bi2O3 as the main components. This scintillating glass contains a large amount of PbO, which seriously pollutes the environment. In addition, this type of scintillating glass has a very low light yield and poor luminous efficiency, which limits its further practical application. Chinese patent CN110734223B discloses a lutetium-based silicate scintillating glass with a glass density exceeding 6.5g / cm 3 , radiation resistance and mechanical strength, but Lu2O3 is expensive and has a radioactive background, making it difficult to use in large scientific facilities.

[0007] Activators in scintillating glasses typically include rare earth luminescence centers, main-group luminescence centers, transition metal luminescence centers, and nanocrystal quantum dots. The optical and scintillation properties of scintillating materials depend largely on the choice of luminescence center and matrix. Among discrete luminescence centers, the luminescence generated by the 5d-4f transition of the cerium ion luminescence center exhibits high light output (spatial resolution) and nanosecond-scale decay times (temporal resolution). Therefore, cerium ion luminescence centers are currently the best activators for scintillating materials. Previous reports have shown that scintillating glass materials doped with luminescence center ions often exhibit only one of the following characteristics: high density, high light yield, and fast decay. These three characteristics are inherently contradictory, often resulting in low light yield in high-density glass and high light yield in low-density glass. The main reasons for this are: first, the high-density glass matrix results in a long absorption cutoff edge, which exacerbates the self-absorption and charge transfer effects of the luminescence center, resulting in low fluorescence intensity; second, high-performance scintillating glass requires a reducing atmosphere to maintain the low valence state of Ce ions, which increases the complexity of equipment and processes, and can also lead to oxidation of some luminescence center ions due to high-temperature feeding and unloading. Therefore, preparing the scintillating glass required for the CEPC hadron calorimeter is a very challenging problem.

[0008] Therefore, the art needs to develop a colorless transparent scintillating glass with high density, high light yield and fast decay time and a preparation method thereof. Summary of the Invention

[0009] In order to solve the above problems, the purpose of the present disclosure is to prepare a colorless and transparent cerium-activated gadolinium aluminum borosilicate fluoride scintillation glass, which has the performance advantages of high density and high light yield and can be used in nuclear radiation detection, high-energy physics experiments, X-ray medical imaging, neutron detection, national security monitoring and other fields.

[0010] The present disclosure provides a cerium-doped gadolinium aluminum borosilicate oxyfluoride scintillating glass, comprising the following components: 16-61.5 mol% Gd2O3, 0-35 mol% GdF3, 1-10 mol% Al2O3, 15-40 mol% B2O3, 5-20 mol% SiO2 and 0.075-6.0 mol% luminescent center compound.

[0011] According to one embodiment of the present disclosure, the content of GdF3 in the scintillating glass is 0-35 mol%, and the content of the trivalent cerium compound is 0.125-6 mol%.

[0012] According to another embodiment of the present disclosure, Al2O3 in the scintillating glass is partially or fully replaced by one or more of AlF3, MgO, MgF2, CaO, CaF2, BaO, BaF, Ga2O3 and GaF3.

[0013] According to another embodiment of the present disclosure, the luminescent center compound is one or more of a trivalent cerium compound, a divalent europium compound, a divalent ytterbium compound, a trivalent terbium compound, a divalent tin compound, a trivalent antimony compound, and a divalent manganese compound; preferably, it is a trivalent cerium compound, and the trivalent cerium compound is one or more of CeF3, Ce2O3 or Ce(NO3)3.

[0014] According to another embodiment of the present disclosure, the scintillating glass further comprises a clarifier; preferably, the clarifier is Sb2O3.

[0015] The present disclosure also provides a method for preparing the cerium-doped gadolinium aluminum borosilicate oxyfluoride scintillating glass, comprising:

[0016] S1: uniformly mixing raw materials for forming the scintillation glass components in a molar ratio to obtain a first mixture, and melting the first mixture at a first predetermined temperature for a first predetermined time by a melting method to obtain molten glass;

[0017] And S2: pouring the molten glass into a mold preheated to a second predetermined temperature for casting, keeping the temperature at the second predetermined temperature for a second predetermined time for annealing, and cooling after annealing to obtain the cerium-doped gadolinium aluminum borosilicate fluoride-oxygen scintillating glass.

[0018] According to one embodiment of the present disclosure, the S1 step is performed in a reducing atmosphere or in a vacuum; alternatively, the S1 step is performed in an air atmosphere, and the raw material for forming SiO2 includes a reducing silicon source, and the reducing silicon source is one or more of Si3N4, SiC, SiO2 or silicon powder.

[0019] According to another embodiment of the present disclosure, the first temperature is 1100-1500° C., and the first predetermined time is 1.5-5.0 hours; the second temperature is 500-800° C., and the second predetermined time is 3.0-6.0 hours.

[0020] According to another embodiment of the present disclosure, in the S2 step, the annealing is carried out at a variable temperature; preferably, the temperature is kept constant at 450-650°C for 2-4 hours, then the temperature is reduced to 200°C at a rate of 5-10°C / minute, and then cooled to room temperature; or, the temperature is kept constant at 450-650°C at a rate of 30-60°C per hour for 2-4 hours, then the temperature is reduced to 200°C at a rate of 5-10°C / minute, and then cooled to room temperature.

[0021] According to another embodiment of the present disclosure, the raw material for forming the trivalent cerium compound is one or more of CeO2, CeF3 or Ce(NO3)3.

[0022] According to another embodiment of the present disclosure, the raw materials for forming B2O3 are one or more of H3BO3, BN, B4C and boron powder.

[0023] According to another embodiment of the present disclosure, the raw material for forming Al2O3 is one or more of Al2O3, AlN, Al(OH)3, AlF3 or aluminum powder.

[0024] The present disclosure further provides an application of gadolinium aluminum borosilicate oxyfluoride scintillating glass in nuclear radiation detection, high energy physics experiments, X-ray medical imaging, neutron detection, and national security monitoring.

[0025] The present invention reduces the melting temperature of glass and the degree of corrosion of crucible by glass solution by partially replacing gadolinium oxide with gadolinium fluoride, thereby increasing the density of glass to 6.0 g / cm 3 Furthermore, the preparation process utilizes a reducing atmosphere, or uses a reducing silicon source to replace or partially replace SiO2, effectively reducing the high-valent luminescent center ions and enabling the preparation of colorless, transparent aluminoborosilicate scintillating glass in an air atmosphere. Furthermore, varying the cerium ion activation concentration improves the scintillation and time performance of the glass, resulting in a light yield exceeding 1000 ph / MeV for the scintillating glass disclosed herein.

[0026] The colorless and transparent cerium-activated gadolinium aluminum borosilicate fluoride scintillation glass prepared in the present invention has a simple preparation process and has the performance advantages of high density and high light yield. Both the density and scintillation performance meet the requirements of the CEPC hadron calorimeter and can be applied to nuclear radiation detection, high-energy physics experiments, X-ray medical imaging, neutron detection, and national security monitoring. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] FIG1 shows optical photographs of the scintillating glasses of Examples 1-8.

[0028] FIG2 shows the X-ray absorption near-edge structure (XANES) spectrum of Example 1.

[0029] FIG3 shows the embodiment 1 in 137 Gamma spectrum under Cs radiation source.

[0030] FIG. 4 shows the transmission spectra of Example 2 and Example 3.

[0031] FIG5 shows the embodiment 2 in 137 Gamma spectrum under Cs radiation source.

[0032] FIG6 shows the embodiment 3 in 137 Gamma spectrum under Cs radiation source.

[0033] FIG7 shows the embodiment 2 and the embodiment 3. 137 Scintillation decay time curve under Cs radiation source.

[0034] FIG8 shows the embodiment 4. 137 Gamma spectrum under Cs radiation source.

[0035] FIG. 9 shows an example of the 137 Scintillation decay time curve under Cs radiation source.

[0036] FIG. 10 shows the embodiment 5. 137 Gamma spectrum under Cs radiation source.

[0037] FIG. 11 shows the embodiment 5. 137 Scintillation decay time curve under Cs radiation source.

[0038] FIG. 12 shows the embodiment 6. 137 Gamma spectrum under Cs radiation source.

[0039] FIG. 13 shows the embodiment 6. 137 Scintillation decay time curve under Cs radiation source.

[0040] FIG. 14 shows the embodiment 7. 137 Gamma spectrum under Cs radiation source.

[0041] FIG. 15 shows the embodiment 7. 137 Scintillation decay time curve under Cs radiation source.

[0042] FIG. 16 shows the embodiment 8. 137 Cs and 22 Gamma spectrum under Na radiation source.

[0043] FIG. 17 shows an example of embodiment 8. 137 Scintillation decay time curve under Cs radiation source. DETAILED DESCRIPTION

[0044] The present disclosure is described in detail below in conjunction with specific implementation methods.

[0045] The cerium-doped gadolinium aluminum borosilicate oxyfluoride scintillating glass disclosed herein comprises 16-61.5 mol% Gd2O3, 0-35 mol% GdF3, 1-10 mol% Al2O3, 15-40 mol% B2O3, 5-20 mol% SiO2, and 0.125-6.0 mol% of a luminescent center compound. The total molar content of each component in the scintillating glass is 100%.

[0046] The present invention uses gadolinium fluoride to partially replace gadolinium oxide, which can reduce the melting temperature of glass and the corrosion of glass solution on crucible, thereby increasing the density of glass to 6.0g / cm 3 and above, which is one of the highest values ​​currently found in borosilicate glass.

[0047] In an optional embodiment, Al2O3 in the scintillating glass may be partially or fully replaced by one or more of AF3, MgO, MgF2, CaO, CaF2, BaO, BaF, Ga2O3, and GaF3.

[0048] In alternative embodiments, the luminescent center compound can be a rare earth luminescent center such as a trivalent cerium compound, a divalent europium compound, or a trivalent terbium compound. The luminescent center compound can also be a transition metal luminescent center such as a divalent tin compound, a trivalent antimony compound, or a divalent manganese compound. Alternatively, it can be one or more of the aforementioned luminescent centers. Preferably, the trivalent cerium compound is one or more of CeF3, Ce2O3, or Ce(NO3)3. The inventors of this disclosure have discovered that by varying the doping level of the luminescent center ion, the light yield and decay time of the scintillator glass can be adjusted to meet the requirements of the CEPC hadron calorimeter.

[0049] In an alternative embodiment, the scintillating glass is doped with 0.125-6.0 mol % of a trivalent cerium compound.

[0050] In an optional embodiment, the scintillating glass further includes a clarifier. Adding the clarifier can reduce bubbles in the glass and improve the performance of the glass. The clarifier can be Sb2O3 or the like.

[0051] The cerium-doped gadolinium aluminum borosilicate oxyfluoride scintillating glass can be prepared by the following preparation method. The preparation method comprises: S1: uniformly mixing raw materials forming scintillating glass components in proportion to obtain a first mixture; melting the first mixture at a first predetermined temperature for a first predetermined time to obtain molten glass; and S2: pouring the molten glass into a mold preheated to a second predetermined temperature for casting, annealing the mold by holding the mold at the second predetermined temperature for a second predetermined time, and cooling the mold after annealing to obtain the cerium-doped gadolinium aluminum borosilicate oxyfluoride scintillating glass.

[0052] Step S1 can be carried out in a reducing atmosphere or in a vacuum. The reducing atmosphere can be an Ar / H2 atmosphere or an N2 / H2 atmosphere. The reducing atmosphere can ensure that the Ce in the prepared glass is trivalent, thereby increasing the probability of radiation transition of the luminescent center in the glass and improving the scintillation performance of the glass. Alternatively, step S1 is carried out in an air atmosphere, and the SiO2 raw material for forming the glass includes a reducing silicon source, and the reducing silicon source is one or more of Si3N4, SiC, SiO or silicon powder. During the preparation process, the tetravalent cerium ions can be reduced to trivalent cerium ions by the reducing silicon source, thereby realizing the preparation of colorless and transparent cerium-doped gadolinium borosilicate scintillating glass in an air atmosphere. The raw materials for forming SiO2 can be all reducing silicon sources, or part of them can be reducing silicon sources and the other part can be SiO2.

[0053] In step S1, the first temperature is 1100-1500°C, the first predetermined time is 1.0-5.0 hours, the second temperature is 500-800°C, the second predetermined time is 1.0-6.0 hours, preferably, the first temperature is 1300-1500°C, and the first predetermined time is 2.0-5.0 hours.

[0054] In an optional embodiment, the raw material for forming the trivalent cerium compound is one or more of CeO2, CeF3 or Ce(NO3)3.

[0055] In an optional embodiment, the raw material for forming B2O3 is one or more of H3BO3, BN, B4C and B powder.

[0056] In an optional embodiment, the raw material for forming Al2O3 is one or more of Al2O3, AlN, Al(OH)3 or Al powder.

[0057] In step S2, the casting process can be performed inside or outside the furnace, resulting in high-performance scintillating glass. Materials such as aluminum bronze and stainless steel can be used to secure the glass. Removing the top and bottom layers of molten glass during the casting process ensures stable glass performance.

[0058] In an optional embodiment, variable temperature annealing can be used. Variable temperature annealing can reduce bubbles in the glass and improve transmittance and scintillation performance. The variable temperature method can be, but is not limited to, maintaining a constant temperature of 450°C to 650°C for 2-4 hours, then cooling the temperature to 200°C at a rate of 5-10°C / minute, and then cooling to room temperature; or, maintaining a constant temperature of 450-650°C at a rate of 30-60°C per hour for 2-4 hours, then cooling the temperature to 200°C at a rate of 5-10°C / minute, and then cooling to room temperature.

[0059] The cerium-doped gadolinium aluminum borosilicate oxyfluoride scintillating glass disclosed herein preferably excludes elements that are radioactive, may interfere with high-energy detection, are toxic, or have coloring properties. For example, Pm and Th are radioactive, La and Lu may interfere with high-energy detection, W can cause coloration during glass preparation, Pb and Tl are toxic during preparation and can discolor the glass under irradiation, and Tb and Eu have long scintillation decay times and are therefore unsuitable for inclusion in the scintillating glass. For cost considerations, high-cost elements such as Lu and Ge may be excluded.

[0060] The cerium-doped gadolinium aluminum borosilicate fluoride-oxygen scintillating glass disclosed herein is used for detecting high-energy particles and is applied in nuclear radiation detection, high-energy physics experiments, X-ray medical imaging, neutron detection, and national security monitoring.

[0061] The present disclosure will be described in detail below with reference to the examples. Unless otherwise specified, the raw materials and equipment used in the examples can be purchased from commercial sources and the operations were carried out under the guidance of the instructions.

[0062] In the following examples, the numerical unit before each component in the glass is mol%. For example, "35Gd2O3" means that the Gd2O3 content in the glass is 35 mol%, and the contents of other components can be deduced in the same way.

[0063] Example 1: Colorless and transparent cerium-doped gadolinium borosilicate scintillating glass 35Gd2O3-23.5GdF3-1Al2O3-22B2O3-18SiO2-0.5CeF3

[0064] High-purity (99.99%) gadolinium oxide (Gd2O3), gadolinium fluoride (GdF3), aluminum oxide (Al2O3), silicon dioxide (SiO2), silicon carbide (SiC), boric acid (H3BO3), and cerium fluoride (CeF3) are weighed according to a stoichiometric ratio and mixed uniformly to prepare a mixture.

[0065] The mixture was transferred to a covered corundum crucible and melted in air at 1300°C for 2.5 hours. The melt was then poured onto a steel plate preheated to 600°C for quenching to form glass.

[0066] The prepared glass was placed in a muffle furnace heated to 600°C for annealing. After keeping the temperature for 3.0 hours, the temperature was lowered to 200°C at a cooling rate of 10°C / min, and then cooled to room temperature in the furnace.

[0067] The colorless and transparent cerium-doped gadolinium borosilicate scintillating glass is obtained by cutting, surface grinding, and polishing the annealed scintillating glass primary product.

[0068] Example 2: Colorless and transparent cerium-doped gadolinium borosilicate scintillating glass 35Gd2O3-23GdF3-1Al2O3-22B2O3-18SiO2-1CeF3

[0069] High-purity (99.99%) gadolinium oxide (Gd2O3), gadolinium fluoride (GdF3), aluminum oxide (Al2O3), silicon dioxide (SiO2), silicon nitride (Si3N4), boric acid (H3BO3), and cerium fluoride (CeF3) are weighed by mole as raw materials, mixed evenly, and prepared into a mixture.

[0070] The mixed raw materials were transferred to a covered corundum crucible and melted in air at a temperature of 1360°C for 3 hours. The melt was poured onto a steel plate preheated to 600°C for quenching to form glass.

[0071] The prepared glass was placed in a muffle furnace heated to 610°C for annealing. After keeping the temperature for 3.0 hours, the temperature was lowered to 200°C at a cooling rate of 10°C / min, and then cooled to room temperature in the furnace.

[0072] The colorless and transparent cerium-doped gadolinium borosilicate scintillating glass is obtained by cutting, surface grinding, and polishing the annealed scintillating glass primary product.

[0073] Example 3: Colorless and transparent cerium-doped gadolinium borosilicate scintillating glass 35Gd2O3-22GdF3-1Al2O3-22B2O3-18SiO2-2CeF3

[0074] High-purity (99.99%) gadolinium oxide (Gd2O3), gadolinium fluoride (GdF3), aluminum oxide (Al2O3), silicon dioxide (SiO2), silicon nitride (Si3N4), boric acid (H3BO3), and cerium fluoride (CeF3) were weighed as raw materials in a molar ratio. The other steps were the same as those in Example 2.

[0075] Example 4: Colorless and transparent cerium-doped gadolinium borosilicate scintillating glass 28Gd2O3-30GdF3-3Ga2O3-18.5B2O3-18.5SiO2-2CeF3

[0076] High-purity (99.99%) gadolinium oxide (Gd2O3), gadolinium fluoride (GdF3), gallium oxide (Ga2O3), silicon dioxide (SiO2), silicon nitride (Si3N4), boric acid (H3BO3), and cerium fluoride (CeF3) were weighed and mixed uniformly in a molar ratio to form a mixture. The mixture was transferred to a covered corundum crucible and melted in an air atmosphere at 1435°C for 6 hours. The melt was poured onto a steel plate preheated to 650°C and quenched to form glass.

[0077] The prepared glass was placed in a muffle furnace heated to 650°C for annealing, and the temperature was reduced by 50°C every hour. After keeping the temperature for 6 hours, the temperature was reduced to 200°C at a cooling rate of 10°C / min, and then cooled to room temperature in the furnace.

[0078] The remaining steps are the same as in Example 2.

[0079] Example 5: Colorless and transparent cerium-doped gadolinium borosilicate scintillating glass 20Gd2O3-33GdF3-15MgF2-20B2O3-5BN-5SiO2-1CeO2

[0080] High-purity (99.99%) gadolinium oxide (Gd2O3), gadolinium fluoride (GdF3), magnesium fluoride (MgF2), silicon dioxide (SiO2), boric acid (H3BO3), boron nitride (BN), and cerium dioxide (CeO2) are weighed as raw materials in a molar ratio, mixed evenly, and prepared into a mixture.

[0081] The mixed raw materials were transferred to a covered corundum crucible and melted in air at a temperature of 1350°C for 4 hours. The melt was poured onto a steel plate preheated to 500°C for quenching to form glass.

[0082] The prepared glass was placed in a muffle furnace heated to 500°C for annealing. After keeping the temperature for 2 hours, the temperature was lowered to 200°C at a cooling rate of 10°C / min, and then cooled to room temperature in the furnace.

[0083] The remaining steps are the same as in Example 2.

[0084] Example 6: Colorless and transparent cerium-doped gadolinium borosilicate scintillating glass 35Gd2O3-23.875GdF3-1Al2O3-22B2O3-18SiO2-0.125CeF3

[0085] The implementation steps are the same as in Example 1.

[0086] Example 7: Colorless and transparent cerium-doped gadolinium borosilicate scintillating glass 32Gd2O3-33GdF3-3AlF3-25B2O3-5SiO2-6CeF3

[0087] The implementation steps are the same as in Example 5.

[0088] Example 8: Colorless and transparent praseodymium-doped gadolinium borosilicate scintillating glass 36Gd2O3-32GdF3-3AlF3-24B2O3-5SiO2-1PrF3

[0089] High-purity (99.99%) gadolinium oxide (Gd2O3), gadolinium fluoride (GdF3), aluminum fluoride (AlF3), silicon dioxide (SiO2), silicon nitride (Si3N4), boric acid (H3BO3), and praseodymium fluoride (PrF3) are weighed as raw materials in a molar ratio, mixed evenly, and prepared into a mixture.

[0090] The implementation steps are the same as in Example 5.

[0091] The scintillating glasses prepared in comparative examples 1-8 were characterized. Optical photographs of the colorless and transparent cerium-doped gadolinium borosilicate scintillating glasses prepared in examples 1-5 were taken with a digital camera. The X-ray absorption near-edge structure (XANES) spectrum of Ce ions was measured on the 1W2B beamline of the Beijing Synchrotron Radiation Facility (BSRF, Beijing, China). A silicon photomultiplier tube (MPPC Hamamatsu, S13360-6050CS, with an effective photosensitive area of ​​6×6 mm2 was used. 2 ) Get the glitter glass in 137 The energy spectrum under Csγ-ray excitation. The light yield and energy resolution of the scintillating glass are further obtained from the energy spectrum. The scintillating glass is obtained using a photomultiplier tube (PMTXP2020, Photonis). 137 The waveform signal under Csγ-ray excitation is used to obtain the scintillation decay time of the glass by averaging the waveform.

[0092] Digital photographs of Examples 1 to 8 are shown in Figure 1. Figure 1 shows, from left to right, optical photographs of the scintillating glasses of Examples 1, 2, 3, 4, 5, 6, 7, and 8. As shown, there are almost no bubbles in the glass, and a small amount of insoluble gadolinium is present on the glass surface. Furthermore, the density of the scintillating glasses produced in all Examples reaches 6.0 g / cm 3 .

[0093] The X-ray absorption near edge structure (XANES) spectrum of Ce ions in Example 1 is shown in FIG2 , which includes standard samples of trivalent and tetravalent Ce compounds (Ce(NO3)3 and CeO2). The energy at 5726 eV corresponds to Ce 3+ 5d→4f transition, and Ce 4+ The oxidation state of Ce has two peaks, located at 5734eV and 5742eV, which are 2p→5d transitions. The XANES spectrum of Example 1 only has Ce. 3+ ion characteristics, which indicates that Ce in the glass 4+ All restored to Ce 3+ Therefore, Example 1 exhibits effective scintillation luminescence.

[0094] Example 1 137 The energy spectrum under Cs gamma-ray excitation is shown in Figure 3. The light yield of Example 1 under gamma-ray excitation is 1076 ph / MeV, with an energy resolution of 49.6% at 662 keV. The light yield of the glass reaches 1000 ph / MeV or above, and a clear full-energy peak can be observed at 662 keV.

[0095] The transmission spectra of Example 2 and Example 3 are shown in FIG4. When the glass matrix composition is the same, as Ce3+ As the concentration increases, the absorption edge of the glass red shifts. 3+ The quenching effect and self-absorption gradually increase, which may lead to the degradation of the scintillation performance of the glass.

[0096] Example 2 137 The energy spectrum under Csγ-ray excitation is shown in Figure 5. From Figure 5, we can clearly see the backscattering peak at about 180keV, which is 137 The gamma rays from the Cs source and the Compton backscattered photons generated by the hard matter around the scintillating glass return to the signal generated by the scintillating glass. At the same time, it can be clearly seen from the figure that 137 The full energy peak of Cs at 662keV indicates that the glass prepared in this embodiment has good scintillation performance. Through Gaussian fitting and calculation, the light yield of Example 2 under gamma rays is 1146ph / MeV, and the energy resolution is 25.1%@662keV.

[0097] Example 3 137 The energy spectrum under Cs gamma-ray excitation is shown in Figure 6. The light yield of Example 3 under gamma-ray excitation is 1070 ph / MeV, with an energy resolution of 24.0% at 662 keV. Due to concentration quenching, the light yield of Example 2 is higher than that of Example 3. However, the energy resolution is increasingly improved. During charge integration, dark noise events from the SiPM are reduced, and statistical errors are reduced, thus improving the energy resolution of the scintillating glass.

[0098] The scintillation decay time curves of Example 2 and Example 3 are shown in FIG7. 137 The decay time curve under Cs radiation source is shown in Figure 7. Through exponential fitting, the scintillation decay times of Example 2 and Example 3 are 119ns (accounting for 5.0%), 894ns and 92ns (accounting for 8.0%), and 473ns respectively. The scintillation glasses of the two examples show two components, fast and slow. The former is attributed to the direct capture of electron-hole pairs in the glass by cerium ions, and the latter comes from Gd 3+ →Ce 3+ Energy transfer process. 3+ As the concentration increases, the Ce-Ce interaction strengthens, the probability of energy transfer between central excited states increases, and the excited electrons are more likely to produce concentration quenching. Therefore, the decay time of the glass is shortened.

[0099] Example 4 137The energy spectrum under Cs gamma-ray excitation is shown in Figure 8. The light yield of Example 4 under gamma-ray excitation is 1019 ph / MeV, with an energy resolution of 27.4% at 662 keV. By modifying the glass heat treatment process, the glass maintains its extremely high optical quality, with significantly fewer internal bubbles. The light yield of Example 4 remains above 1000 ph / MeV.

[0100] Example 4 137 The decay time curve under a Cs radiation source is shown in Figure 9. After fitting and calculation, the decay time is 103.8 (4.4%), 764.8 ns. Due to the changes in the heat treatment process, defects in the glass have slightly increased, increasing the probability of electron-hole pair capture by these defects. Consequently, the slow component in the glass decay time has increased.

[0101] Example 5 137 The energy spectrum under Csγ-ray excitation is shown in Figure 10. The light yield of Example 5 under gamma ray is 884ph / MeV, and the energy resolution is 31.2%@662keV. Using MgF2 as a network intermediate to replace Al2O3 in the glass increases the optical alkalinity of the glass, which makes Ce in the glass 3+ The self-absorption effect is aggravated, which eventually leads to a decrease in the scintillation performance of Example 5, and the light yield is around 900ph / MeV.

[0102] Example 5 137 The decay time curve under a Cs radiation source is shown in Figure 11, with decay times of 80.8 (4.9%) and 1251.2 ns, respectively. The ionic radius / molar volume of the alkaline earth metal oxide affects the decay time of the glass; the larger the ionic radius, the longer the decay time. Therefore, Example 5 exhibits a relatively long decay time, with the slow component exceeding 1000 ns.

[0103] Example 6 137 The energy spectrum under Csγ-ray excitation is shown in Figure 12. The light yield of Example 6 under gamma ray is 1044ph / MeV, and the energy resolution is 26.8%@662keV. This proves that low concentration Ce 3+ Doped scintillating glasses also have a higher light yield.

[0104] Example 6 137 The decay time curve under Cs radiation source is shown in Figure 13, and its decay time is 1091.0ns. 3+ Doping, the scintillation decay time of the glass is longer.

[0105] Example 7 137The energy spectrum under Csγ-ray excitation is shown in Figure 14. The light yield of Example 7 under gamma ray is 696ph / MeV, and the energy resolution is 41.8%@662keV. 3+ For doped scintillating glass, due to concentration quenching, the light yield of the glass decreases to around 700ph / MeV.

[0106] Example 7 137 The decay time curve under the Cs radiation source is shown in Figure 15, with a decay time of 287.0 ns. Due to the concentration quenching of excited electrons, the scintillation decay time of the glass is very short, less than 300 ns.

[0107] Example 8 137 Cs and 22 The energy spectrum under Naγ-ray excitation is shown in Figure 16. The light yield of Example 8 under gamma ray is 610ph / MeV, and the energy resolution is 42.9%@662keV. Example 8 proves that Pr 3+ Doped gadolinium borosilicate glass also has good scintillation properties.

[0108] Example 8 137 The decay time curve under Cs radiation source is shown in Figure 17. The decay times are 147.6 (60.9%) and 1486.1 ns respectively. The former is attributed to the direct capture of electron-hole pairs in the glass by praseodymium ions, and the latter is attributed to the capture of electron-hole pairs in the glass by Gd ions. 3+ →Pr 3+ energy transfer process.

[0109] The preferred embodiments of the present disclosure disclosed above are intended only to help illustrate the present disclosure. The preferred embodiments do not describe all details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present disclosure, thereby enabling those skilled in the art to better understand and utilize the present disclosure. The present disclosure is limited only by the claims and their full scope and equivalents.

Claims

1. A gadolinium aluminum borosilicate fluoride oxyscintillating glass, characterized in that: The scintillation glass comprises the following components: 16-61.5 mol% Gd2O3, 0-35 mol% GdF3, 1-10 mol% Al2O3, 15-40 mol% B2O3, 5-20 mol% SiO2 and 0.125-6.0 mol% of the luminescent center compound.

2. The gadolinium aluminum borosilicate oxyfluoride scintillating glass according to claim 1, characterized in that: The content of GdF3 in the scintillating glass is 0 to 35 mol%.

3. The gadolinium aluminum borosilicate fluoride oxyscintillating glass according to claim 1 or 2, characterized in that: The Al2O3 in the scintillating glass is partially or completely replaced by one or more of AlF3, MgO, MgF2, CaO, CaF2, BaO, BaF2, Ga2O3, and GaF3.

4. The gadolinium aluminum borosilicate oxyfluoride scintillating glass according to any one of claims 1 to 3, characterized in that: The luminescent center compound is one or more of a trivalent cerium compound, a divalent europium compound, a trivalent terbium compound, a divalent tin compound, a trivalent antimony compound, and a divalent manganese compound; preferably, it is a trivalent cerium compound, and the trivalent cerium compound is one or more of CeO2, CeF3 and Ce2O3.

5. The gadolinium aluminum borosilicate oxyfluoride scintillating glass according to any one of claims 1 to 4, characterized in that: The scintillating glass further comprises a clarifier, such as antimony oxide and sodium nitrate; preferably, the clarifier is antimony oxide.

6. A method for preparing the gadolinium aluminum borosilicate fluoride oxyscintillating glass according to any one of claims 1 to 5, characterized in that: include: S1: uniformly mixing raw materials for forming the scintillation glass components in a molar ratio to obtain a first mixture, and melting the first mixture at a first predetermined temperature for a first predetermined time by a melting method to obtain a molten glass liquid; and S2: pouring the molten glass into a mold preheated to a second predetermined temperature for casting, and maintaining the temperature at the second predetermined temperature for a second predetermined time for annealing to obtain the gadolinium aluminum borosilicate fluoride oxygen scintillation glass.

7. The preparation method according to claim 6, characterized in that: The S1 step is performed in a reducing atmosphere or in a vacuum; alternatively, the S1 step is performed in an air atmosphere, and the raw material for forming SiO2 includes a reducing silicon source, and the reducing silicon source is one or more of Si3N4, SiC, SiO or silicon powder.

8. The preparation method according to claim 6 or 7, characterized in that: The first temperature is 1100-1500° C., and the first predetermined time is 1.0-5.0 hours; the second temperature is 500-800° C., and the second predetermined time is 1.0-6.0 hours.

9. The preparation method according to any one of claims 6 to 8, characterized in that: In the step S2, the annealing is performed at a variable temperature; preferably, the temperature is kept constant at 450-650°C for 2-4 hours, then the temperature is reduced to 200°C at a cooling rate of 5-10°C / min, and then cooled to room temperature; or, the temperature is kept constant at 450-650°C for 2-4 hours, then the temperature is reduced to 200°C at a cooling rate of 5-10°C / min, and then cooled to room temperature.

10. The preparation method according to any one of claims 6 to 9, characterized in that: The raw materials for forming B2O3 are one or more of H3BO3, BN, B4C and B powder.

11. The preparation method according to any one of claims 6 to 10, characterized in that: The raw materials for forming Al2O3 are one or more of Al2O3, AlN, Al(OH)3, AlF3 or Al powder.

12. The gadolinium aluminum borosilicate fluoride oxygen scintillating glass according to any one of claims 1 to 5 is used for detecting high-energy particles, and is used in nuclear radiation detection, high-energy physics experiments, X-ray medical imaging, neutron detection, and national security monitoring.

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