Glass scintillator and preparation method and application thereof
The preparation of glass scintillators by high-temperature melting method solves the difficulties in serving the existing scintillators in extreme environments and the multiple problems existing in the preparation of traditional scintillators, and realizes the preparation of glass scintillators with large area, excellent resolution and low cost, which is suitable for X-ray imaging in extreme environments.
Patent Information
- Application Number
- CN202510201835.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-24
- Publication Date
- 2025-05-27
AI Technical Summary
The existing scintillators have difficulty in serving in extremely harsh environments, and the preparation of traditional scintillators has problems such as difficulty in preparing large areas uniformly, severe self-absorbing effects, poor resolution and high cost.
Using a high-temperature melting method, the quaternary phosphine salt and antimony trichloride are mixed and heated to obtain a molten substance, and then covered on the surface of the preheated glass substrate to prepare a glass scintillator.
It realizes the preparation of glass scintillator with large area, excellent resolution and low cost, and can be served for a long time in extreme environments, expanding the application range of X-ray glass scintillator materials.
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Abstract
Description
Technical Field
[0001] This application relates to the technical field of scintillator preparation, and particularly to a glass scintillator, a preparation method thereof, and an application thereof. Background Art
[0002] Currently, the classic scintillators in service (CsI:Tl, CdS, CsPbBr 3 ) are limited by the problem of poor stability and can only be used in relatively mild scenarios, such as medical imaging, industrial imaging, security inspection, and other mild environments at room temperature, low humidity, and low dose. However, the demand for ray detectors in key national fields such as aviation, navigation, and the nuclear industry for use in extremely harsh environments is urgent, and there is an urgent need to develop a scintillator for use in extreme environments (high temperature, high humidity, high light, high radiation).
[0003] Due to its dense and stable glass network structure, scintillating glass has stability that cannot be matched by other forms of scintillators (scintillating crystals, scintillating organics, scintillating ceramics), and thus has been widely studied and tracked by scholars at home and abroad. The currently developed scintillating glasses are mainly divided into perovskite microcrystalline glasses and rare earth ion microcrystalline glasses. Although the problem of their stability has been solved, there are still the following problems: (1) It is difficult to prepare uniformly over a large area, with a complex nucleation thermodynamics and growth kinetics process, and it is difficult to nucleate and grow uniformly over a large area; (2) It has a serious self-absorption effect (Pb-based), an electron transition forbidden effect (f-transition rare earth-based), defect trap energy loss, and a narrow full width at half maximum of the emission spectrum and other processes that are not conducive to luminescence; (3) The resolution is poor. Since the glass phase and the luminescent phase components in the scintillating glass differ too much, the refractive index mismatch is too large, which exacerbates the refraction and scattering of the light path; (4) The cost is high, containing expensive elements such as alkali metal Cs and rare earth metals Ce, etc. Therefore, there is an urgent need to prepare a glass scintillator with a large area, excellent resolution, and low cost to enable long-term service in extreme environments. Summary of the Invention
[0004] This application provides a glass scintillator, a preparation method thereof, and an application thereof to solve the following technical problems: providing a preparation method for a glass scintillator.
[0005] In a first aspect, an embodiment of this application provides a preparation method for a glass scintillator, the method comprising:
[0006] Mix a quaternary phosphonium salt and antimony trichloride, and heat and melt them at a set temperature to obtain a molten substance;
[0007] Preheat a glass substrate so that the temperature of the glass substrate is the same as the temperature of the molten substance;
[0008] Cover the molten material on the surface of the preheated glass substrate to obtain a glass scintillator.
[0009] Optionally, the quaternary phosphonium salt includes at least one of the following: triphenylmethylphosphonium chloride, triphenylethylphosphonium chloride, triphenylpropylphosphonium chloride, triphenylbutylphosphonium chloride.
[0010] Optionally, the molar ratio of the quaternary phosphonium salt to the antimony trichloride is 2:1.
[0011] Optionally, the set temperature is 240°C to 300°C.
[0012] Optionally, the set temperature is 280°C.
[0013] Optionally, the holding time for heating and melting is 10 min to 20 min.
[0014] Optionally, the preheating temperature is 260°C to 280°C.
[0015] Optionally, the resolution of the glass scintillator is not less than 19.0 lp / mm.
[0016] In a second aspect, an embodiment of the present application provides a glass scintillator, which is prepared by the method described in any one of the embodiments of the first aspect.
[0017] In a third aspect, an embodiment of the present application provides an application of the glass scintillator described in any one of the embodiments of the second aspect in X-ray imaging.
[0018] The above technical solutions provided by the embodiments of the present application have the following advantages compared with the prior art:
[0019] The preparation method of the glass scintillator provided by the embodiment of the present application includes: mixing a quaternary phosphonium salt with antimony trichloride, heating and melting at a set temperature to obtain a molten substance; preheating a glass substrate to make the temperature of the glass substrate the same as that of the molten substance; covering the molten substance on the surface of the preheated glass substrate to obtain a glass scintillator. By using the high-temperature melting method to prepare the glass scintillator, it avoids the time-consuming and laborious regulation of the complex nucleation thermodynamics and kinetics processes of traditional microcrystalline glass scintillator materials and the uneconomical addition of Cs sources, can realize the preparation of large-area X-ray glass scintillator materials and reduce production costs. Moreover, the preparation method of the present invention has the characteristics of simple operation, short time, and controllable thickness, which can greatly promote the industrial production of large-area X-ray glass scintillator materials. The resolution of the glass scintillator is not less than 19.0 lp / mm. Compared with traditional microcrystalline glass, the preparation method of this glass scintillator material has a high transmittance, and at the same time makes the luminescent phase evenly dispersed, ensuring the uniform luminescence of the glass. In addition, glass scintillator materials with different areas and thicknesses and strong stability and uniformity can be prepared, enabling them to serve for a long time in extreme environments and expanding the application range of X-ray glass scintillator materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The drawings herein are incorporated into the specification and constitute a part of this specification, showing embodiments consistent with the present application, and are used together with the specification to explain the principles of the present application.
[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.
[0022] Figure 1 It is a schematic flowchart of a preparation method of a glass scintillator provided by an embodiment of the present application;
[0023] Figure 2 It is a physical diagram of a glass scintillator provided by an embodiment of the present application;
[0024] Figure 3 It is a transmittance test chart of a glass scintillator provided by an embodiment of the present application;
[0025] Figure 4 It is a resolution test chart of a glass scintillator provided by an embodiment of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0026] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the following will clearly and completely describe the technical solutions in the embodiments of this application with reference to the accompanying drawings in the embodiments of this application. Obviously, the described embodiments are some, but not all, of the embodiments of this application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in this application without creative efforts fall within the scope of protection of this application.
[0027] The various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be construed as a rigid limitation on the scope of this application; therefore, it should be considered that the described range description has specifically disclosed all possible sub-ranges and single values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.
[0028] In this application, unless otherwise stated, the orientation terms such as "upper" and "lower" specifically refer to the drawing directions in the accompanying drawings. Additionally, in the description of this application specification, the terms "include", "comprise", etc. mean "including but not limited to". In this document, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. In this document, "at least one" means one or more, and "a plurality" means two or more. "At least one kind", "at least one of the following (items)", or similar expressions refer to any combination of these items, including any combination of single (item) or plural items (items). For example, "at least one of (item) a, b, or c", or, "at least one of (item) a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, c can be single or multiple respectively. The "parts representation method" such as parts by weight, parts by mass, etc. represents the proportional relationship between components. In the proportional relationships involved in this document, the parameters that need to be described by proportion should be understood as the antecedents of the proportion formula in the order of description, and the proportional numbers should be understood as the consequents of the proportion formula. For example, if the mass ratio of substance A, substance B, and substance C is 1:2:3, then substance A, substance B, and substance C should correspond one by one with the proportional numbers in the proportion formula in the order of description, that is, the mass of substance A: the mass of substance B: the mass of substance C = 1:2:3.
[0029] Unless otherwise specified, various raw materials, reagents, instruments, and equipment used in this application can be obtained through market purchases or can be prepared by existing methods.
[0030] In a first aspect, an embodiment of the present application provides a method for preparing a glass scintillator. Figure 1 It is a schematic flow chart of a method for preparing a glass scintillator provided by an embodiment of the present application; please refer to Figure 1 , the method includes:
[0031] S1. Mix a quaternary phosphonium salt with antimony trichloride and heat and melt it at a set temperature to obtain a molten substance.
[0032] A glassy scintillator is a scintillator material in a glassy state. When irradiated with high-energy rays (such as X-rays, γ-rays, etc.) or particles (such as electrons, protons, etc.), it can convert the absorbed energy into visible light or near-visible light and emit it.
[0033] Compared with other types of scintillators, glassy scintillators have the following main advantages: Easy adjustment of chemical composition: The chemical composition of glassy scintillators can be easily adjusted, which enables them to customize their luminescence characteristics according to specific application requirements. This flexibility provides a broad space for optimizing the performance of scintillators. Good optical uniformity: Glass scintillators have good optical uniformity, which means that their optical properties are consistent in all directions, which is crucial for ensuring the uniform response of detectors. Easy to achieve large sizes: Glass scintillators can be easily prepared in large sizes, which is very important for applications that require large-area detectors (such as medical imaging, security inspections, etc.). Large-size scintillators can provide a larger detection area and improve detection efficiency. Simple preparation method: The preparation method of glass scintillators is relatively simple, which helps to reduce production costs and improve production efficiency. The simple preparation process also makes it easier for glass scintillators to achieve large-scale production. Excellent processing performance: Glass composite scintillators have excellent processing performance and can be manufactured into various shapes and sizes, including blocks and tiny fibers, which provides great flexibility for design and manufacturing. Low cost: The production cost of glass scintillators is relatively low, which makes them more competitive in cost-sensitive applications. These advantages make glassy scintillators have broad application prospects in many fields such as high-energy physics, nuclear medicine, and industrial detection.
[0034] Mix the quaternary phosphonium salt with antimony trichloride and heat it to melt at a set temperature to obtain a molten substance. This step determines the starting materials and the preliminary treatment method, preparing for the subsequent combination with the glass matrix. In the embodiments of this application, with the help of the thermal uniform diffusion of ions in molten glass at a set temperature, there is no need to finely control numerous complex factors as in traditional methods. Thermal uniform diffusion is based on the natural movement characteristics of ions at high temperatures. As long as appropriate high-temperature conditions are maintained, ions can diffuse relatively uniformly in molten glass, thus simplifying the preparation process and greatly saving time and energy costs.
[0035] In some embodiments, the quaternary phosphonium salt includes at least one of the following: triphenylmethylphosphonium chloride, triphenylethylphosphonium chloride, triphenylpropylphosphonium chloride, triphenylbutylphosphonium chloride.
[0036] The quaternary phosphonium salt can be a combination of one or more of triphenylmethylphosphonium chloride, triphenylethylphosphonium chloride, triphenylpropylphosphonium chloride, and triphenylbutylphosphonium chloride.
[0037] In some embodiments, the molar ratio of the quaternary phosphonium salt to the antimony trichloride is 2:1.
[0038] In the chemical preparation process, the molar ratio of raw materials often plays a decisive role in the progress of the reaction, the purity and structure of the product, etc. Mixing the quaternary phosphonium salt and antimony trichloride in a molar ratio of 2:1 can promote an ideal chemical reaction between them (2C 19 H 18 PCl + SbCl 3 →(C 19 H 18 P) 2 SbCl 5 ), which helps to generate the target product and reduce the occurrence of side reactions, thereby improving the product quality and consistency. This precise proportional relationship will affect the performance of the final glass scintillator. For example, it may affect the microscopic properties such as the crystal structure inside the material, the formation of chemical bonds, and the electron cloud distribution, and further affect the macroscopic properties such as the optical properties (such as luminescence efficiency, light transmittance, etc.) and chemical stability of the glass scintillator.
[0039] In some embodiments, the set temperature is 240°C to 300°C.
[0040] In some embodiments, the set temperature is 280°C.
[0041] The set temperature can be 240°C to 300°C. The quaternary phosphonium salt and antimony trichloride can obtain sufficient energy to overcome the activation energy of the reaction, enabling the chemical reaction between them to proceed smoothly. The appropriate temperature range provides an appropriate reaction rate. This temperature range can cause the quaternary phosphonium salt and antimony trichloride to melt sufficiently to form a uniform molten substance. Only in the completely molten state can they mix better with each other, achieving a uniform distribution at the molecular level and creating good conditions for subsequent bonding with the glass matrix. The glass matrix usually has a certain thermal stability and softening temperature range. Controlling the heating temperature of the quaternary phosphonium salt and antimony trichloride at 240°C to 300°C can make the temperature of the molten substance adapt to that of the glass matrix after the glass matrix is preheated, facilitating better bonding between the two. Temperature has an important influence on the crystal structure and microstructure of the final glass scintillator. In the temperature range of 240°C to 300°C, it is conducive to forming an ideal crystal structure and microstructure, enabling the luminescent phase to be evenly dispersed in the glass matrix, thereby improving the optical properties of the glass scintillator, such as luminescence efficiency, light uniformity, etc. The appropriate temperature range helps to ensure the stability of the glass scintillator material. And based on the material properties of the quaternary phosphonium salt and antimony trichloride, compared with the melting temperature of the prior art, this glass scintillator realizes low-temperature melting preparation. Exemplarily, the set temperature can be 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, etc.
[0042] In some embodiments, the holding time for heating and melting is 10 min to 20 min.
[0043] The holding time for heating and melting can be 10 min to 20 min. Sufficient holding time can ensure the full reaction of the quaternary phosphonium salt and antimony trichloride. Appropriate holding time helps the reaction to proceed uniformly throughout the system. During the holding process of 10 min to 20 min, the quaternary phosphonium salt and antimony trichloride can melt sufficiently and mix with each other, making the whole system reach a uniform molten state. Appropriate holding time helps to optimize the microstructure of the glass scintillator. The holding time of 10 min to 20 min can ensure more stable performance of the glass scintillator prepared in different batches. Exemplarily, the holding time for heating and melting can be 10 min, 12 min, 14 min, 16 min, 18 min, 20 min, etc.
[0044] S2. Preheat the glass matrix so that the temperature of the glass matrix is the same as that of the molten substance;
[0045] Preheat the glass matrix to the same temperature as the molten substance to ensure temperature matching when the two are combined, which is conducive to the subsequent fusion process.
[0046] In some embodiments, the preheating temperature is 260°C to 280°C.
[0047] The preheating temperature can be 260°C to 280°C. This preheating temperature range corresponds to the temperature (240°C to 300°C) after the quaternary phosphonium salt and antimony trichloride are heated and melted, ensuring that when the glass substrate contacts the molten material, the temperature difference between the two is within a reasonable range. At 260°C to 280°C, the physical state of the glass substrate is more conducive to fusing with the molten material. This temperature range can cause a certain degree of adjustment to the internal structure of the glass substrate. The atomic arrangement inside the glass will become more orderly, eliminating some internal stresses, thereby enhancing the stability of the glass substrate. Appropriately raising the temperature of the glass substrate to 260°C to 280°C can activate the chemical active sites on the glass surface to a certain extent, which helps the molten material to have a more effective chemical reaction with the glass substrate, making the combination of the two more firm, forming a more stable chemical bond at the interface, and thus enhancing the mechanical properties and optical properties of the glass scintillator. The preheating temperature within this range is coordinated with the subsequent step of covering the molten material on the surface of the glass substrate. Exemplarily, the preheating temperature can be 260°C, 265°C, 270°C, 275°C, 280°C, etc. The glass substrate can be one of quartz glass, FTO glass, and ITO glass.
[0048] S3. Cover the surface of the preheated glass substrate with the molten material to obtain a glass scintillator.
[0049] Cover the molten material on the surface of the preheated glass substrate to obtain a glass scintillator. This process realizes the forming of the material.
[0050] In some embodiments, the resolution of the glass scintillator is not less than 19.0 lp / mm.
[0051] The embodiment of the present application provides a preparation method of a glass scintillator, which has the following advantages:
[0052] 1. Process simplification and cost reduction: By using the high-temperature melting method, it avoids the complexity of regulating the complex nucleation thermodynamics and kinetics processes in the preparation of traditional microcrystalline glass scintillator materials, and there is no need to add uneconomical Cs sources. It can not only realize the preparation of large-area X-ray glass scintillator materials, but also reduce the production cost;
[0053] 2. Convenient and efficient operation: It has the characteristics of simple operation and short time consumption, which can improve the production efficiency and reduce the labor cost in actual production;
[0054] 3. Controllable product parameters: It can achieve controllable thickness, enabling the product to meet different requirements in terms of thickness specifications, and further enhancing the flexibility of product application;
[0055] 4. Glass scintillator characteristics: High resolution: The resolution is not less than 19 lp / mm, meeting the requirements for imaging clarity and other aspects in specific application scenarios. Superior optical performance: Compared with traditional microcrystalline glass, this preparation method endows the material with high transmittance, while making the luminescent phase evenly dispersed, ensuring uniform luminescence of the glass and enhancing the optical performance of the material. Strong size adaptability and stability: Glass scintillator materials with different areas and thicknesses can be prepared, and their stability is strong, enabling them to serve for a long time in extreme environments, expanding the application scope of X-ray glass scintillator materials and meeting the needs of more special scenarios.
[0056] In the second aspect, embodiments of the present application provide a glass scintillator prepared by the method according to any one of the embodiments in the first aspect.
[0057] This glass scintillator is realized based on the above-mentioned preparation method of the glass scintillator. The specific steps of the preparation method of this glass scintillator can refer to the above embodiments. Since this glass scintillator adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments, which will not be elaborated one by one here.
[0058] In the third aspect, embodiments of the present application provide an application of the glass scintillator according to any one of the embodiments in the second aspect in X-ray imaging.
[0059] This application of the glass scintillator in X-ray imaging is realized based on the above-mentioned glass scintillator. The specific preparation steps of this glass scintillator can refer to the above embodiments. Since this application of the glass scintillator in X-ray imaging adopts some or all of the technical solutions of the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments, which will not be elaborated one by one here.
[0060] The following further elaborates the present application in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present application and not to limit the scope of the present application. The experimental methods without specific conditions noted in the following embodiments are usually determined according to national standards. If there is no corresponding national standard, they are carried out according to general international standards, conventional conditions or conditions recommended by the manufacturer.
[0061] Example 1
[0062] S1. Mix the quaternary phosphonium salt and antimony trichloride, and heat and melt them at a set temperature to obtain a molten substance;
[0063] Specifically: (1) Raw material weighing: Weigh triphenylmethylphosphonium chloride and antimony trichloride raw materials with a molar ratio of 2:1 into a sample bottle respectively. (2) Semi-sealing treatment: Seal the sample bottle with tin foil, and pierce three to five small holes in the tin foil with a 1 mL syringe needle to allow the bubbles in the molten material to volatilize and escape. (3) Heating and melting: Place the sample bottle of the mixed system in a muffle furnace at 280 °C and heat until the raw materials are completely melted, and keep warm for 15 min.
[0064] S2. Preheat the glass substrate ITO glass so that the temperature of the glass substrate is the same as that of the molten material;
[0065] Specifically: Place the pretreated glass sheet on a hot stage at 270 °C for preheating so that the temperature of the molten material is the same as that of the glass substrate.
[0066] S3. Cover the surface of the preheated glass substrate with the molten material to obtain a glass scintillator.
[0067] Specifically: Quickly drop and coat the molten material onto the glass substrate so that the glass sheet is covered with the molten material, and keep warm for 15 min to ensure that the bubbles therein are removed. Finally, obtain a transparent glassy scintillator film, and place the scintillator film in a transparent acrylic floating film storage box and store it in a drying cabinet away from light.
[0068] Figure 2 This is a physical diagram of a glass scintillator provided by an embodiment of the present application; please refer to Figure 2 , and it can be seen that the glass scintillator is pure. Figure 3 This is a transmittance test diagram of a glass scintillator provided by an embodiment of the present application; Figure 4 This is a resolution test diagram of a glass scintillator provided by an embodiment of the present application; please refer to Figures 3 - 4 , indicating that the glass scintillator has high transmittance and high X-ray spatial imaging resolution and can serve for a long time in extreme environments. Note: "Transmittance(%)" means "transmittance (%)", "Wavelength(nm)" means "wavelength (nanometer)"; "Modulation transfer function" is common in the fields of optics, image processing, etc., and means "modulation transfer function" to evaluate imaging performance, "Spatial resolution(lp mm -1) " means "spatial resolution (line pairs per millimeter).
[0069] One or more technical solutions in the embodiments of the present application at least further have the following technical effects or advantages:
[0070] (1) It overcomes the problems of traditional inorganic bulk scintillators, such as being limited by high-temperature synthesis, difficult to be prepared on a large area of flexible substrates, and high cost.
[0071] (2) It realizes a scintillator preparation process that optimizes the large-area preparation process, optimizes the resolution, and reduces the cost, and can serve for a long time in extreme environments.
[0072] The above are only specific embodiments of the present application, enabling those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but rather will be accorded the widest scope consistent with the principles and novel features claimed herein.
Claims
1. A method for preparing a glass scintillator, the method comprising: The quaternary phosphonium salt and antimony trichloride are mixed and heated to melt at a set temperature to obtain a molten substance; preheating the glass matrix so that the temperature of the glass matrix is the same as the temperature of the molten substance; The molten material is covered on the surface of the preheated glass substrate to obtain a glass scintillator.
2. The method according to claim 1, characterized in that The quaternary phosphonium salt comprises at least one of triphenylmethylphosphonium chloride, triphenylethylphosphonium chloride, triphenylpropylphosphonium chloride, and triphenylbutylphosphonium chloride.
3. The method according to claim 1, characterized in that The molar ratio of the quaternary phosphonium salt to the antimony trichloride is 2:
1.
4. The method according to claim 1, characterized in that: The set temperature is 240°C to 300°C.
5. The method according to claim 4, characterized in that The set temperature is 280°C.
6. The method according to claim 1, 4 or 5, characterized in that: The heat preservation time of the heating and melting is 10 minutes to 20 minutes.
7. The method according to claim 1, characterized in that The preheating temperature is 260°C to 280°C.
8. The method according to claim 1, characterized in that: The resolution of the glass scintillator is not less than 19.0 lp / mm.
9. A glass scintillator, wherein the glass scintillator is prepared by the method according to any one of claims 1 to 8.
10. Use of the glass scintillator according to claim 9 in X-ray imaging.