Terbium-fluoride-oxide glass scintillator, method of preparation and use thereof

Abstract

The application belongs to the field of optical functional materials and detection applications, and relates to a terbium-doped fluorine-oxygen glass scintillator. The application discloses a terbium-doped fluorine-oxygen glass scintillator, which comprises the following components in terms of molar percentage: SiO2: 45-60%, Al2O3: 0-10%, MgF2: 2-10%, NaF: 2-15%, Na2CO3: 1-10%, B2O3: 0-15%, CaCO3: 0-10%, SrCO3: 0-10%, BaCO3: 0-10%, and TbF3: 0-5%. 3+ The application can adjust the terbium-doped fluorine-oxygen glass scintillator by adjusting the concentration of alkali earth metal, the ratio of B2O3 / Al2O3 or TbF3. The material in the application can be customized according to specific applications, thereby expanding the potential application market. The terbium-doped fluorine-oxygen glass scintillator has better performance than traditional scintillation crystals, and is expected to occupy part of the scintillator market by virtue of cost and performance advantages, and has high commercial value and practicability.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic functional materials and detection applications, specifically terbium-doped fluorine oxide glass scintillator, its preparation method and its application. Background Technology

[0002] Scintillators have the ability to convert high-energy X-ray photons into low-energy ultraviolet / visible light, and are widely used in fields such as nuclear medicine imaging, industrial non-destructive testing, environmental monitoring and security inspection.

[0003] In related technologies, inorganic crystal materials are the main type of scintillator. However, these crystals are not only expensive and time-consuming to prepare, but also have complex processes. In addition, these scintillators suffer from low luminous efficiency and luminous afterglow, thus limiting their spatial resolution in X-ray imaging.

[0004] Glass, with its designable mechanical properties, thermal stability, and chemical stability, has become one of the best candidate materials for scintillators. Fluoro-oxygen glass combines the advantages of oxide glasses (such as good stability) and fluoride glasses (such as low phonon energy), making it a favored material for scintillators. Terbium ion emission spectra are highly compatible with CCD or silicon detectors, and its lifetime reaches the millisecond level, making it ideal for high-resolution imaging. Therefore, terbium-doped fluoro-oxygen glass scintillators exhibit some advantages. However, in the process of commercialization, terbium-doped fluoro-oxygen glass scintillators still have some problems or shortcomings, such as the inability to control scintillation performance or the limited methods for controlling scintillation performance. For example, energy transfer methods can be used to modulate scintillation performance. J. Appl. Phys., 119, 233103 (2016) reported on the modulation of scintillation performance of terbium-doped fluorine-oxygen glass through terbium / dysprosium co-doping, while Ceram. Int., 49, 15500 (2023) and J. Lumin., 245, 118762 (2022) reported on the modulation of scintillation performance of terbium-doped fluorine-oxygen glass through cerium / terbium co-doping. However, these methods are limited by the concentration and uniformity of the co-doped ions, resulting in a limited range of modulation. Furthermore, the scintillator cannot be customized according to application requirements and scenarios, which greatly restricts the application scope and potential of terbium-doped fluorine-oxygen glass scintillators. Summary of the Invention

[0005] The purpose of this disclosure is to provide a terbium (Tb)-doped fluorine-oxygen glass scintillator that improves X-ray detection efficiency and imaging resolution to a certain extent.

[0006] According to one aspect of this disclosure, a terbium (Tb) fluorine-oxygen-doped glass scintillator is provided, comprising: glass for providing a luminescent environment for a luminescent center; and the terbium for serving as a luminescent center.

[0007] According to another aspect of this disclosure, a method for improving scintillation performance by controlling the glass composition is provided, wherein the control strategies include, but are not limited to, controlling the alkaline earth metal, the B2O3 / Al2O3 ratio, or Tb. 3+ Methods such as concentration.

[0008] A terbium-doped fluorine-oxygen glass scintillator comprises the following components in molar percentage: SiO2: 45-60%, Al2O3: 0-10%, MgF2: 2-10%, NaF: 2-15%, Na2CO3: 1-10%, B2O3: 0-15%, CaCO3: 0-10%, SrCO3: 0-10%, BaCO3: 0-10%, TbF3: 0-5%.

[0009] Furthermore, the terbium-doped fluorine-oxygen glass scintillator has the following chemical structural formulas: SiO2-Al2O3-CaCO3-MgF2-NaF-Na2CO3-yTbF3, SiO2-Al2O3-SrCO3-MgF2-NaF-Na2CO3-yTbF3, and SiO2-Al2O3-BaCO3-MgF2-NaF-Na2CO3-yTbF3, wherein 0 <y<5。

[0010] Furthermore, the terbium-doped fluorine-oxygen glass scintillator has the chemical structural formula SiO2-(10-x)Al2O3-xB2O3-BaCO3-MgF2-NaF-Na2CO3-yTbF3, where 0 <x<10,0<y<5。

[0011] Furthermore, this invention provides a component control strategy to regulate the scintillation properties of terbium-doped fluorine-oxygen glass.

[0012] This invention also provides a method for preparing a terbium-doped fluorine-oxygen glass scintillator, comprising the following steps: (1) Weigh SiO2, Al2O3, MgF2, NaF, Na2CO3, B2O3, CaCO3, SrCO3, BaCO3, and TbF3 raw materials, mix them thoroughly to obtain mixed raw material powder, and transfer them to a high-temperature resistant crucible; (2) Place the crucible from step (1) in a high temperature, melt it in the air for a period of time, then cast the melt into a mold at a specific temperature, and quench it to obtain a block glass. (3) The block glass obtained in step (2) is subjected to stress relief treatment, and after natural cooling, it is cut, ground and polished to obtain terbium-doped fluorine-oxygen glass scintillator.

[0013] Furthermore, in step (2), the melting temperature is 1300-1450℃ and the melting time is 1-3 hours.

[0014] Furthermore, the temperature is increased to 1300-1450℃ at a heating rate of 3-10℃ / min.

[0015] Furthermore, in step (2), the mold temperature is 280-350℃.

[0016] Furthermore, the stress relief temperature in step (3) is 300-400℃.

[0017] Furthermore, the stress relief time in step (3) is 3-24 hours.

[0018] This invention also provides an application of terbium-doped fluorine-oxygen glass scintillator in the field of X-ray imaging.

[0019] Based on the above technical solutions and the technical problems solved, the advantages and positive effects of the technical solution to be protected by this invention are as follows: First, this invention provides a component regulation strategy for optimizing the preparation and performance of terbium-doped fluorine-oxygen glass, which serves as the theoretical basis for the preparation, performance optimization, and industrial promotion of terbium-doped fluorine-oxygen glass scintillators.

[0020] Secondly, this invention provides detailed steps and parameters for terbium-doped fluorine-oxygen glass, providing technical support for terbium-doped fluorine-oxygen glass and its control.

[0021] Third, compared to traditional crystal scintillators, the raw materials, preparation method, and preparation cycle used in this invention have significant cost advantages. As a mature industry, scintillators are widely used in hospitals, security checks, scientific research, and factory testing, and the market demand for scintillators is increasing, with the global market share maintaining a double-digit growth rate year after year. The terbium-doped fluorine-oxygen glass scintillator provided by this invention has superior performance compared to traditional scintillator crystals and is expected to capture a portion of the scintillator market due to its cost and performance advantages, possessing high commercial value and practicality.

[0022] Fourth, the significant technological advancements achieved by the terbium-doped fluorine-oxygen glass scintillator provided by this invention include the following aspects: 1) The X-ray excitation fluorescence intensity of terbium-doped glass scintillators is typically lower than that of scintillating crystals. This invention, by controlling the composition of fluorine-oxygen glass, achieves an X-ray excitation fluorescence intensity in terbium-doped glass scintillators that far exceeds that of crystal scintillators. This is crucial for energy conservation and improved equipment performance.

[0023] 2) The emission peak of terbium ions is located near 542 nm, which is very consistent with commercial CCD or silicon detectors. This helps to realize X-ray imaging or detection and provides a wider range of applications.

[0024] 3) Tunable X-ray excitation of fluorescence: This can be achieved by adjusting the alkaline earth metal, B2O3 / Al2O3 ratio, or Tb. 3+The concentration can be adjusted to control the intensity of X-ray excited fluorescence in the scintillator. This means that the materials in this invention can be customized for specific applications, expanding their potential market.

[0025] 4) Potential stability and durability: The material in this invention has high X-ray radiation stability and thermal stability, and can operate under more demanding conditions, which is important for commercialization.

[0026] 5) Cost effect: The preparation method, preparation cycle and cost of the scintillator provided by this invention have great advantages over crystal scintillators. From an economic point of view, it has a great cost advantage, which is also important for large-scale production and commercial promotion. Attached Figure Description

[0027] Figure 1 A flowchart illustrating the preparation method of a terbium-doped fluorine-oxygen glass scintillator provided in an embodiment of the present invention.

[0028] Figure 2 The transmission spectrum of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 1 of the present invention is shown.

[0029] Figure 3 The image shows the X-ray excitation fluorescence spectrum of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 1 of this invention.

[0030] Figure 4 The transmission spectrum of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 2 of the present invention is shown.

[0031] Figure 5 The image shows the X-ray excitation fluorescence spectrum of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 2 of this invention.

[0032] Figure 6 The transmission spectrum of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 3 of the present invention is shown.

[0033] Figure 7 The image shows the X-ray diffraction pattern of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 3 of this invention.

[0034] Figure 8 The lifetime curve of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 3 of the present invention is shown.

[0035] Figure 9 The image shows the X-ray excitation fluorescence spectrum of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 3 of this invention.

[0036] Figure 10 This diagram illustrates the application of the terbium-doped fluorine-oxygen glass scintillator prepared in Example 3 of this invention in the field of X-ray detection. Detailed Implementation

[0037] The following are embodiments of the present invention. It should be noted that these embodiments are more detailed descriptions of certain aspects, characteristics, and implementation schemes of the present invention, and are not intended to limit the scope of the invention. The present invention is not limited to the following embodiments. Unless otherwise specified, the methods described are conventional methods.

[0038] A terbium (Tb)-doped fluorine-oxygen glass scintillator comprises the following components in molar percentage: SiO2: 45-60%, Al2O3: 0-15%, MgF2: 2-13%, NaF: 2-15%, Na2CO3: 1-10%, B2O3: 0-15%, CaCO3: 0-10%, SrCO3: 0-10%, BaCO3: 0-10%, TbF3: 0-5%.

[0039] The chemical structural formulas of terbium (Tb)-doped fluorine-oxygen glass scintillators are: SiO2-Al2O3-CaCO3-MgF2-NaF-Na2CO3-yTbF3, SiO2-Al2O3-SrCO3-MgF2-NaF-Na2CO3-yTbF3, SiO2-Al2O3-BaCO3-MgF2-NaF-Na2CO3-yTbF3, and SiO2-(10-x)Al2O3-xB2O3- Any one of BaCO3-MgF2-NaF-Na2CO3-yTbF3, wherein 0 <x<10,0<y<5。

[0040] This invention provides a composition control strategy to regulate the scintillation performance of terbium-doped fluorine-oxygen glass.

[0041] like Figure 1 As shown, the present invention also provides a method for preparing terbium-doped fluorine-oxygen glass, comprising the following steps: (1) Accurately weigh high-purity SiO2, Al2O3, MgF2, NaF, Na2CO3, B2O3, CaCO3, SrCO3, BaCO3, TbF3 and other raw materials, mix them thoroughly to obtain mixed raw material powder, and transfer them to a high-temperature resistant crucible; (2) Place the crucible from step (1) in a high temperature, melt it in the air for a period of time, then cast the melt into a mold at a specific temperature, and quench it to obtain a block glass. (3) The block glass obtained in step (2) is subjected to stress relief treatment, and after natural cooling, it is cut, ground and polished to obtain terbium-doped fluorine-oxygen glass scintillator; In step (2), the melting temperature is 1300-1450℃ and the melting time is 1-3 hours; In step (2), the mold temperature is 280-350℃; In step (3), the stress relief temperature is 300-400℃ and the stress relief time is 3-24 hours; This invention also provides the application of terbium-doped fluorine-oxygen glass scintillators in the field of X-ray imaging.

[0042] The following describes the process through more specific embodiments.

[0043] Example 1 In this embodiment, the scintillators obtained are 58SiO2-12Al2O3-10CaCO3-7MgF2-8NaF-3Na2CO3-2TbF3, 58SiO2-12Al2O3-10SrCO3-7MgF2-8NaF-3Na2CO3-2TbF3, and 58SiO2-12Al2O3-10BaCO3-7MgF2-8NaF-3Na2CO3-2TbF3.

[0044] The method for preparing terbium-doped fluorine-oxygen glass involved in this embodiment is as follows: Step S11: Weigh the raw materials SiO2, Al2O3, MgF2, NaF, Na2CO3, B2O3, CaCO3, SrCO3, BaCO3, and TbF3 according to the above molar percentages, mix them thoroughly in a mortar, and then transfer them to an alumina crucible. Step S12: Transfer the crucible to a high-temperature furnace and heat it to 1400°C at a heating rate of 5°C / min. Melt it in the air for 2 hours. Immediately remove the crucible and pour the molten liquid in the crucible into a mold. Set the mold temperature to 300°C. After quenching, obtain block glass. Step S13: Transfer the block glass obtained above to a low-temperature furnace, set the furnace temperature to 300°C, and hold it for 24 hours to relieve stress. After natural cooling, cut, grind, and polish to obtain the terbium-doped fluorine-oxygen glass scintillator in Example 1.

[0045] Example 2 In this embodiment, the scintillator obtained is 55SiO2-(10-x)Al2O3-xB2O3-10BaCO3-6-MgF2-6NaF-2Na2CO3-2TbF3, where x=0, 5, 10. The preparation method of the terbium-doped fluorine-oxygen glass involved in this embodiment is as follows: Step S21: Weigh the raw materials SiO2, Al2O3, MgF2, NaF, Na2CO3, B2O3, BaCO3, and TbF3 according to the above molar percentages, mix them thoroughly in a mortar, and then transfer them to an alumina crucible. Step S22: Transfer the crucible to a high-temperature furnace and heat it to 1420°C at a heating rate of 5°C / min. Melt it in the air for 1.5 hours. Immediately remove the crucible and pour the molten liquid in the crucible into a mold. Set the mold temperature to 300°C. After quenching, obtain block glass. Step S23: Transfer the block glass obtained above to a low-temperature furnace, set the furnace temperature to 300°C, and hold it for 24 hours to relieve stress. After natural cooling, cut, grind, and polish to obtain the terbium-doped fluorine-oxygen glass scintillator in Example 2.

[0046] Example 3 In this embodiment, the scintillator obtained is 55SiO2-5Al2O3-5B2O3-10BaCO3-6-MgF2-6NaF-2Na2CO3-yTbF3, where y = 0.4, 0.8, 1.5, 2, 2.5, 3, 5. The preparation method of the terbium-doped fluorine-oxygen glass involved in this embodiment is as follows: Step S31: Weigh the raw materials SiO2, Al2O3, MgF2, NaF, Na2CO3, B2O3, BaCO3, TbF3, etc. according to the above molar percentages, mix them thoroughly in a mortar, and then transfer them to an alumina crucible. Step S32: Transfer the crucible to a high-temperature furnace and heat it to 1420°C at a heating rate of 5°C / min. Melt it in the air for 1.5 hours. Immediately remove the crucible and pour the molten liquid in the crucible into a mold. Set the mold temperature to 300°C. After quenching, obtain block glass. Step S33: Transfer the block glass obtained above to a low-temperature furnace, set the furnace temperature to 300°C, and hold it for 24 hours to relieve stress. After natural cooling, cut, grind, and polish to obtain the terbium-doped fluorine-oxygen glass scintillator in Example 3.

[0047] Example 1 describes the preparation of terbium-doped fluorine-oxygen glass using alkaline earth metal oxides (CaCO3, SrCO3, BaCO3). Figure 2 The transmittance of the glass obtained in Example 1 is from... Figure 2 As can be seen above, the transmittance of glass can be controlled by adjusting the alkaline earth metal oxides. Among them, CaCO3-based glass exhibits the best transmittance. Figure 3 The X-ray excitation fluorescence spectrum of the glass obtained in Example 1 is from... Figure 3 As can be seen above, the X-ray excitation emission of the scintillator can be controlled by regulating the alkaline earth metal oxides. Among them, the BaCO3-based glass exhibits the best X-ray excitation emission intensity. Furthermore, the X-ray excitation emission intensity of the three different alkaline earth metal-based glasses obtained in Example 1 is stronger than that of the conventional crystalline BGO, indicating that these glasses have practical application potential. This ability to control scintillation emission through alkaline earth metals allows the scintillator to be customized for specific applications.

[0048] Example 2 describes how to adjust the B2O3 / Al2O3 ratio to control scintillation performance. Figure 4 To obtain the transmittance of the glass in Example 2, from Figure 4As can be seen above, the transmittance of the glass was improved and increased with the addition of B2O3. Figure 5 The X-ray excitation emission spectrum shows that the intensity of X-ray excitation emission of the scintillator can be controlled by adjusting the B2O3 / Al2O3 ratio. Furthermore, the glass obtained in Example 2 exhibits a stronger X-ray excitation emission intensity than the crystal scintillator, indicating the material's excellent scintillation performance. By adjusting the B2O3 / Al2O3 ratio to control the scintillation performance, this material can be customized to meet different application requirements, i.e., it can be tailored to specific application scenarios.

[0049] Example 3 describes how to adjust the concentration of luminescent center ions to achieve scintillation performance control. Figure 6 To obtain the transmittance of the glass in Example 3, from Figure 6 As can be seen from Tb 3+ With increasing concentration, the transmittance of the glass remained essentially unchanged. Meanwhile, Tb 3+ The increase in concentration did not cause crystallization inside the glass, such as Figure 7 As shown. Example 3 yielded glass with a lifetime of 3.49 ms, which is essentially independent of Tb. 3+ Concentration changes, such as Figure 8 As shown. The millisecond-level lifetime makes these glass scintillators suitable for high-resolution imaging and slow X-ray detection. Figure 9 The X-ray excitation emission spectrum of the glass obtained in Example 3 is from... Figure 9 It can be seen from this that regulating Tb 3+ Concentration can modulate its X-ray excitation luminescence intensity, with the maximum luminescence intensity reaching 219.8% of that of scintillation crystals. Table 1 shows the concentrations of different Tb values. 3+ The comparison of X-ray excitation intensity of high-concentration doped glass with that of scintillation crystals indicates that Tb-doped glass can be used to achieve high-concentration X-ray emission. 3 + Concentration-controlled scintillation performance; on the other hand, compared with scintillation crystals, the terbium-doped glass scintillator provided by this invention is important for energy saving and improving equipment performance.

[0050] Table 1 Comparison of the radiation fluorescence intensity of the scintillator and the scintillator crystal in Example 3

[0051] Application Examples. To demonstrate the inventiveness and technical value of the technical solution of the present invention, this section provides application examples of the technical solution of the claims on specific products or related technologies.

[0052] The present invention prepares a terbium-doped fluorine-oxygen glass scintillator, which can be used to detect X-rays and achieve X-ray imaging. For example, using the glass sample in Example 3, the scintillator can be integrated between the sample and the detector to achieve X-ray imaging of the sample.

[0053] Evidence of the effects of the embodiments. The embodiments of the present invention have achieved some positive effects during the research and development or use process, and do have significant advantages compared with the prior art. The following content describes them in conjunction with the data, figures, etc. of the experimental process.

[0054] Using the glass from Example 3 as the scintillator material, the imaging capability of the aforementioned terbium-doped fluorine-oxygen glass scintillator was verified using a self-made X-ray imaging device. Figure 10 As shown, based on the scintillator of this invention, the internal details of the circuit board can be clearly seen. When a spring is placed inside a capsule, under X-ray irradiation, the scintillator of this invention can clearly display an image of the spring inside the capsule. The spatial imaging resolution of this scintillator reaches 16 lp / mm, exceeding that of most crystal scintillators and glass scintillators, and possesses commercial viability. Based on this invention, by adjusting the glass basicity, B2O3 / Al2O3 ratio, and Tb... 3+ Concentration can be used to further regulate scintillation performance, such as spatial imaging resolution.

[0055] The above descriptions are merely two specific embodiments of the present invention, which also include other embodiments. The lead-free glass-ceramic scintillator described in this invention possesses excellent optical and scintillation properties, making it suitable for applications such as medical imaging, nuclear detection, and high-energy physics experiments.

[0056] The above description is merely a specific embodiment of the present invention for better understanding. 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 terbium-doped fluorine-oxygen glass scintillator, characterized in that: The composition includes the following components by molar percentage: SiO2: 45-60%, Al2O3: 0-10%, MgF2: 2-10%, NaF: 2-15%, Na2CO3: 1-10%, B2O3: 0-10%, CaCO3: 0-10%, SrCO3: 0-10%, BaCO3: 0-10%, TbF3: 0.8-5%; The Al2O3 is not 0, and the CaCO3, SrCO3, and BaCO3 are not all 0 at the same time; The preparation method of the terbium-doped fluorine-oxygen glass scintillator includes the following steps: (1) Weigh SiO2, Al2O3, MgF2, NaF, Na2CO3, B2O3, CaCO3, SrCO3, BaCO3, and TbF3 raw materials, mix them thoroughly to obtain mixed raw material powder, and transfer them to a high-temperature resistant crucible; (2) Place the crucible from step (1) in a high temperature, melt it in the air for a period of time, then cast the melt into a mold at a specific temperature, and quench it to obtain a block glass. (3) The block glass obtained in step (2) is subjected to stress relief treatment, and after natural cooling, it is cut, ground and polished to obtain terbium-doped fluorine-oxygen glass scintillator; In step (2), the melting temperature is 1300-1450℃ and the melting time is 1-3 hours; Heating to 1300-1450℃ at a heating rate of 3-10℃ / min; In step (2), the mold temperature is 280-350℃; The stress relief temperature in step (3) is 300-400℃; The stress relief time in step (3) is 3-24 hours.

2. An application of the terbium-doped fluorine-oxygen glass scintillator according to claim 1 in the field of X-ray imaging.

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