Preparation method of reconfigurable glass scintillation screen and application of reconfigurable glass scintillation screen in X-ray co-formation imaging

Abstract

The invention provides a preparation method of a reconfigurable glass scintillation screen and application of the reconfigurable glass scintillation screen in X-ray co-formation imaging, and belongs to the technical field of X-ray imaging, and the preparation method specifically comprises the following steps: raw material pre-synthesis, high-temperature melting, glass scintillation screen forming and reconstruction processing. The problems that a commercial scintillator in a flat plate type X-ray detector is high in processing difficulty, the shape of the commercial scintillator is not plastic, the commercial scintillator cannot be conformal with a measured object with an irregular shape and the like are effectively solved, and meanwhile, the problems of light scattering and transmittance reduction in a conventional polymer-doped flexible scintillation screen are solved. The shape of the glass scintillation screen can give full play to the reconfigurable characteristic of the glass scintillation screen, the glass scintillation screen is processed according to the shape of a measured object, conformal X-ray imaging is further completed under the condition that the shape of the object changes continuously, the problem of imaging distortion caused by non-conformal imaging is effectively solved, and the imaging resolution is high.

Description

Technical Field

[0001] The invention belongs to the technical field of X-ray imaging, and relates to a method for preparing a reconfigurable glass scintillating screen and its application in X-ray co-forming imaging. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Nondestructive testing technology can effectively provide information about the internal structure of the object being tested without damaging or changing the intrinsic physical or chemical state of the object, thus providing strong data support for the development of various industries. Among the many nondestructive testing technologies, radiation detection based on X-rays is one of the key technologies, and its application range covers from industrial detection to clinical diagnosis. X-ray detectors are an important part of X-ray radiation detection systems. Whether they are direct detectors using semiconductors such as silicon (Si), α-selenium (α-Se), cadmium zinc telluride (CdZnTe), or thallium-doped cesium iodide (CsI:Tl + ), bismuth germanate (Bi 4 Ge 3 O 12 ), lutetium yttrium silicate ((Lu, Y) 2 SiO 5 ) and other scintillators, most of which are currently used in the form of flat-panel detectors. This type of flat-panel detector can be suitable for most application scenarios. However, when flat-panel detectors are used for X-ray imaging of objects with irregular shapes, the image details are blurred and distorted. For example, when performing industrial inspections on internal cracks in aircraft engines or broken circuits in electronic chips, flat-panel detectors are prone to omissions of complex structural information; in medical diagnosis of physiological parts with complex spatial structures such as the head, joints, and chest cavity, the images provided by flat-panel detectors cannot enable doctors to fully understand the fine structures and potential lesions deep inside.

[0004] In addition, by collecting images from different directions and combining them with computer reconstruction algorithms, three-dimensional images of objects can be constructed. However, the increase in radiation dose caused by multiple X-ray exposures is a worrying problem, especially when X-rays are used to detect human lesions. Taking all factors into consideration, X-ray coform imaging provides the best solution to the above problems. In X-ray coform imaging, the close fit between the imaging detector and the geometric contour of the object to be inspected can effectively solve the image distortion problem and provide information such as the internal structure, size, and defect location of the object, thereby achieving accurate detection. Therefore, for X-ray coform imaging, shape-adjustable detectors are required to match various irregularly shaped objects. Considering that traditional inorganic scintillators and semiconductors have high hardness and are only conducive to the processing of planar detectors, researchers have developed a series of flexible detectors to adapt to the surfaces of objects with irregular shapes. Among them, doped nanocrystalline polymer films and doped ground powder polymer films are the most common. By using a series of lead-based (Pb(II)), copper-based (Cu(I)), and manganese-based (Mn(II)) metal halides as guest dopants and polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA) or cellulose as the host, the prepared flexible scintillating screen shows certain advantages in X-ray curved surface imaging. However, the above-mentioned flexible scintillating screen also has the following disadvantages: (1) the organic host containing light elements and the luminescent guest containing heavy elements with low doping concentration have low absorption capacity for X-rays; (2) the large-sized solid particles and the aggregation of nanocrystals inside the doped film will cause uneven radiation luminescence intensity and light scattering (Rayleigh scattering, Mie scattering), resulting in low transmittance and spatial imaging resolution of the doped film.

[0005] In order to overcome the above problems, glass materials with high transparency and uniformity become the preferred candidates. Usually, inorganic scintillating glass is prepared by high-temperature sintering (greater than 1000°C), and the experimental conditions required are relatively harsh. In contrast, organic-inorganic hybrid scintillating glass prepared under mild conditions (about 200°C) has more advantages. At the same time, organic-inorganic hybrid glass contains a large volume of organic components, which makes it difficult to crystallize during high-temperature quenching. Therefore, it has attracted great attention from researchers, such as using divalent manganese combined with organic phosphine derivatives or guanidine derivatives, monovalent copper combined with organic phosphine derivatives, and trivalent antimony (Sb(III)) combined with organic phosphine derivatives to prepare organic-inorganic hybrid scintillating glass, all of which show high transmittance, high light yield and high spatial imaging resolution. However, the organic-inorganic hybrid scintillating glass reported so far is still focused on the flat type. Researchers have also tried to make it into a curved scintillating screen for non-planar X-ray imaging. "Organic–Inorganic Hybrid Mn-Based Transparent Glass for Curved X-RayScintillation Imaging" discloses a plastic perovskite glass scintillator, but it requires a mold and special extrusion molding to make a curved screen. Not only is the preparation method complicated, but it also cannot meet the requirements for diversified matching of irregularly shaped objects.

[0006] In summary, the shapes of objects in real life are endless and even constantly changing, and reconfigurable scintillator screens for X-ray coform imaging in different or changing application scenarios have not yet been explored. Summary of the invention

[0007] In view of the shortcomings of the prior art, in order to overcome the high processing difficulty of commercial scintillators as the main functional layer of X-ray flat panel detectors, the difficulty in realizing reconstructed processing and diversified matching with objects with irregular shapes to further meet the needs of refined imaging, and the problems of uneven scintillation light intensity, light scattering, low transmittance, etc. in conventional doped flexible scintillator screens, the present invention provides a method for preparing a reconstructible glass scintillator screen and its application in X-ray co-forming imaging. The present invention makes full use of the characteristics of low glass transition temperature, good chemical stability and thermal stability of organic-inorganic hybrid scintillator glass to perform reconstructed processing to match objects with irregular shapes and perform high-resolution X-ray co-forming imaging.

[0008] In order to achieve the above object, the present invention adopts the following technical solution:

[0009] A first aspect of the present invention provides a method for preparing a reconfigurable glass scintillating screen, comprising:

[0010] placing the organic-inorganic hybrid material in a mold to melt it, thereby obtaining a mold with a melt;

[0011] The mold with the melt is quenched and demoulded to obtain a glass scintillating screen;

[0012] The glass scintillator screen is heated to soften it, and then matched with the shape of the imaging object, and solidified and formed again to obtain;

[0013] Among them, the organic component of the organic-inorganic hybrid material is an organic phosphine derivative, a guanidine derivative, etc., and the inorganic component is a metal halide salt, such as (TPT) 2 MnB 4 、(3Br-TPT) 2 MnB 4 or (TPT) 2 ZnBr 4 , and this type of organic-inorganic hybrid material should meet the glass transition temperature (T g )<Crystallization temperature (T x )<Melting point(T m )<Decomposition point(T d ) and glass transition temperature (T g ) / Melting point(T m )>0.67 is a prerequisite.

[0014] The present invention utilizes the fact that part of the organic-inorganic hybrid scintillating glass has a lower glass transition temperature (T g ), good thermal stability and chemical stability, thus giving the organic-inorganic hybrid scintillating glass a reconfigurable property.

[0015] In some embodiments, the method for synthesizing the organic-inorganic hybrid material comprises: uniformly mixing an organic raw material and an inorganic raw material, and then grinding the mixture to obtain an organic-inorganic hybrid material;

[0016] Preferably, the grinding time is 30 min-2 h, or the raw material is placed in a planetary ball mill for grinding, the swing frequency is set to 20-40 times / second, and the duration is maintained at 30 min-1 h;

[0017] In some embodiments, an organic solvent is added to the raw material, preferably at least one of n-hexane, cyclohexane, dichloromethane, chloroform, methanol, ethanol, and acetone.

[0018] In some embodiments, after grinding, the raw material is observed to see whether its color changes or irradiated with light of wavelengths of 365 nm or 254 nm to see whether the synthesized raw material emits fluorescence at a specific wavelength, thereby verifying whether the reaction is complete.

[0019] Preferably, in step (2), the grinding time can be 20 min, 40 min, 1 h, 1.5 h, 2 h, etc. according to the reaction conditions of the raw materials. The ball mill swing frequency is set to 20 times / second, 30 times / second, 40 times / second, 50 times / second, etc. The ball milling time can be maintained at 30 min, 40 min, 50 min, 1 h, etc. The organic solvent takes an appropriate volume, such as 3 mL, 5 mL, 7 mL, 9 mL, 11 mL, 13 mL, 15 mL, etc. At the same time, when irradiated with an ultraviolet flashlight, the newly synthesized raw material will emit fluorescence of a specific wavelength, such as green light, yellow light, orange light, etc.

[0020] In some embodiments, the mold is a square silicone mold, a circular silicone mold, a triangular silicone mold, a diamond silicone mold, a trapezoidal silicone mold, or a parallelogram silicone mold.

[0021] In some embodiments, the square silicone mold has a side length of 1 cm to 25 cm, preferably 1±0.1 cm, 3±0.1 cm, 6±0.1 cm, 9±0.1 cm, 12±0.1 cm, 15±0.1 cm, 18±0.1 cm, 20±0.1 cm, 22±0.1 cm, 24±0.1 cm, 25±0.1 cm;

[0022] In some embodiments, the rectangular silicone mold has a long side length of 5 cm to 45 cm, preferably 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm, 40±0.1 cm, 45±0.1 cm; the short side length is 1 cm to 35 cm, preferably 1±0.1 cm, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm;

[0023] In some embodiments, the circular silicone mold has an inner diameter of 2 cm to 35 cm, preferably 2±0.1 cm, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm;

[0024] In some embodiments, the triangular silicone mold has three sides of 5 cm to 35 cm, preferably 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm;

[0025] In some embodiments, the diamond-shaped silicone mold has a diamond side length of 5 cm to 35 cm, preferably 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm;

[0026] In some embodiments, the trapezoidal silicone mold has an upper bottom side length of 5 cm to 20 cm, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, and a lower bottom side length of 10 cm to 35 cm, preferably 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm;

[0027] In some embodiments, a parallelogram-shaped silicone mold, wherein two parallel sides are 5 cm to 35 cm, preferably, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm, and the other two parallel sides are 5 cm to 35 cm, preferably, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm;

[0028] In some embodiments, the wall thickness of the silicone mold is 0.1 cm to 0.5 cm, preferably, 0.1±0.05 cm, 0.15±0.05 cm, 0.2±0.05 cm, 0.25±0.05 cm, 0.3±0.05 cm, 0.35±0.05 cm, 0.4±0.05 cm, 0.45±0.05 cm, 0.5±0.05 cm;

[0029] In some embodiments, the groove depth of the silicone mold is 0.5 cm to 5 cm, preferably, 0.5±0.05 cm, 1±0.05 cm, 1.5±0.05 cm, 2±0.05 cm, 3±0.05 cm, 4±0.05 cm.

[0030] In some embodiments, the temperature of the heating oven is set in the range of 180°C-270°C, preferably 180±1°C, 190±1°C, 200±1°C, 210±1°C, 220±1°C, 230±1°C, 240±1°C, 250±1°C, 260±1°C, 270±1°C. If there are bubbles in the melt, it can be slightly shaken, or the oven can be vacuumed to remove the bubbles to prevent the bubbles from being solidified inside the glass during the quenching process, resulting in light scattering and reducing the quality of X-ray imaging. At the same time, the demolding should be handled with care to prevent the glass scintillator from breaking.

[0031] In some embodiments, the quenching treatment is performed at room temperature.

[0032] In some embodiments, the reconstructing process is performed by heating at a glass transition temperature (Tg) ± 10°C.

[0033] By utilizing the good thermal and chemical stability of the glass scintillator, it can be re-melted near the melting point to match the imaging object of different shapes. In some embodiments, the re-molded shape is constructed according to the imaging object, including various geometric shapes, preferably, rectangle, square, circle, trapezoid, triangle, rhombus, parallelogram;

[0034] By utilizing the glass scintillator screen's glass transition temperature, the shape of the object to be imaged can be repeatedly reconstructed into different shapes near the glass transition temperature, not limited to the shapes and specifications described below. In some embodiments, the reconstructed glass scintillator screen has a bending angle of 10° to 80°, preferably 10±1°, 20±1°, 30±1°, 40±1°, 50±1°, 60±1°, 70±1°, 80±1°. The rectangular glass scintillator screen can also be bent and fitted to the imaging object, and the specific bending condition is determined by the imaging object.

[0035] More specifically, they include:

[0036] (1) Raw material weighing: In order to prevent impurities from affecting the luminescent properties of the organic-inorganic hybrid glass scintillator, it is necessary to purchase high-purity monomer raw materials or purify the commercial monomer raw materials by multiple solution methods, gas phase methods, and zone melting methods. Subsequently, the organic components and inorganic components used are weighed according to a certain stoichiometric ratio. The stoichiometric ratio of organic components to inorganic components needs to be determined according to the composition of the target material, such as 1:1, 1:2, 1:3, 1:4, 2:1, 2:3, etc. Because some raw materials may be hygroscopic, the weighing of the raw materials should be carried out in a glove box with trace moisture and an inert atmosphere to avoid stoichiometric imbalance and deviation in raw material synthesis.

[0037] (2) Raw material presynthesis: The weighed raw materials with a specific ratio are placed in an agate mortar for full grinding. In order to allow the two raw materials to fully react, the grinding time is maintained at 30min-2h or the raw materials are placed in a planetary ball mill for grinding, with the swing frequency set at 20-40 times / second and the duration maintained between 30min-1h. In addition, in order to allow the raw materials to fully contact, a small amount of volatile organic solvents such as n-hexane, cyclohexane, dichloromethane, chloroform, methanol, ethanol, acetone, etc. can be added thereto. After grinding, observe whether the color of the raw materials changes or illuminate them with an ultraviolet flashlight with a wavelength of 365nm or 254nm. You can see that the newly synthesized raw materials emit fluorescence at a specific wavelength, so as to verify whether the reaction is complete.

[0038] (3) High-temperature melting of raw materials: After the fully ground raw materials are placed in a silicone mold of a specific size, they are placed in a high-temperature oven for melting. The heating temperature should be between the melting point and decomposition point of the material to prevent the temperature from being too high and causing oxidation and decomposition of the material. When performing high-temperature melting, protection should be taken to prevent burns. The raw materials need to be maintained at high temperature for a period of time to ensure that the solid particles are completely transformed into a melt with a characteristic color. In addition, the size of the silicone mold used should be customized according to the experimental requirements, and its processing size and processing style are diverse.

[0039] (4) Forming of glass scintillator screen: Take the stabilized melt out of the high-temperature oven and use the huge temperature difference between the melting temperature and the room temperature as the driving force for quenching. Do not touch or shake it manually during the cooling process. After a few minutes, a glass scintillator screen with a certain shape can be obtained.

[0040] (5) Reconstruction processing of glass scintillator screen: Taking advantage of its good thermal and chemical stability, it can be re-melted and reshaped to match imaging objects of different shapes. Alternatively, it can be placed in an oven at a specific temperature for heating, and the temperature should be set near the glass transition temperature. After a few minutes, it softens and can be repeatedly processed into different shapes to match imaging objects of different shapes.

[0041] (6) X-ray co-form imaging of glass scintillator screen: An X-ray co-form imaging system was built using a commercial X-ray source, an imaging object, a reconstructed glass scintillator screen, an optical reflector, a commercial digital camera, and a radiation-proof lead plate, and the imaging effect was tested.

[0042] Preferably, in step (1), the inorganic component is a metal halide salt, and the raw material purity of 99%, 99.9%, 99.99%, and 99.999% can meet the requirements.

[0043] Preferably, in step (1), the organic component is an organic molecule with good thermal stability such as an organic phosphine derivative or a guanidine derivative.

[0044] Preferably, in step (1), when the commercial monomer raw material is purified by solution method, a suitable solvent should be selected, such as toluene, m-xylene, p-xylene, isopropanol, acetonitrile, etc. The temperature used for gas phase purification should be 10-50°C lower than the melting point of the material. The temperature used for zone melting purification should be 10-50°C higher than the melting point of the material.

[0045] Preferably, in step (6), the X-ray source, the optical reflector and the imaging digital camera are all commercially available.

[0046] The second aspect of the present invention provides a reconfigurable glass scintillating screen prepared by the above method.

[0047] The third aspect of the present invention provides the use of the above-mentioned reconfigurable glass scintillator screen in X-ray coform imaging.

[0048] Beneficial Effects of the Invention

[0049] (1) The raw materials used in the present invention are low-priced, which is very conducive to the large-area preparation of organic-inorganic hybrid glass scintillating screens.

[0050] (2) The present invention makes full use of the good thermal stability and chemical stability and low glass transition temperature of glass materials to achieve the reconstruction of glass scintillator screens. It effectively overcomes the disadvantages of using flat panel detectors, achieves the goal of X-ray co-formation imaging with objects with irregular shapes, and further meets the needs of refined imaging.

[0051] (3) The present invention uses a glass scintillating screen for X-ray co-forming imaging, which can effectively avoid problems such as light scattering caused by solid particles, low transmittance of thin doped films, and low imaging resolution.

[0052] (4) The preparation method of the present invention is simple, practical and easy to promote. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention, and the exemplary embodiments of the present invention and their description are used to explain the present invention and do not constitute improper limitations on the present invention.

[0054] Figure 1 This is a photo of a rectangular glass scintillating screen prepared using a rectangular silicone mold in Example 1 of the present invention.

[0055] Figure 2The characterization of the rectangular glass scintillator in Example 1 of the present invention is as follows: (A) a large-area organic-inorganic hybrid glass scintillator screen (20×20 cm) prepared by melt-quenching method at room temperature 2 ); (B) is (TPT) 2 MnB 4 The diffraction patterns of crystals, glass powders and (TPT) 2 MnB 4 Simulated powder diffraction pattern of (TPT) grown using the antisolvent diffusion method. 2 MnB 4 Crystal. (C) is (TPT) 2 MnB 4 Load-displacement curves of glass and crystal at room temperature and 55°C. Cyclic test at room temperature for six times, load 5000μN; at 55°C for (TPT) 2 MnB 4 The glass was tested three times with a load of 100 μN and a test interval of 5 minutes. (D) is (TPT) 2 MnB 4 A magnified image of the results of three cycles of testing glass at 55°C. (E) The load-bearing condition of a bent glass screen (7cm×2cm×1.5mm) at room temperature under 100g (1); the load-bearing condition of a bent glass screen at 55°C under 10g (2); and the flat glass screen manually bent into different complex shapes at 55°C (3)-(4).

[0056] Figure 3 The reconstructed processing of Example 1 of the present invention: (A) is at 220°C (TPT) 2 MnB 4 Schematic diagram of the glass remelting and molding process. (B) is the remelting and molding of different shapes (TPT) 2 MnB 4 Glass. (C) Yes (TPT) 2 MnB 4 Schematic diagram of the conformal processing of glass at 55°C. (D) is (TPT) 2 MnB 4 The glass was heated at 55°C and conformed to toy balls of different diameters (6 cm to 9 cm). The top photo shows the conformal photo of the glass scintillator and the toy ball, and the bottom photo shows the corresponding reconstructed glass. (E) is (TPT) 2 MnB 4 The glass is heated at 55°C and processed conformally to the different shapes of the Magic Ruler. The top photo shows the conformal glass scintillator and Magic Ruler, and the bottom photo shows the corresponding reconstructed glass.

[0057] Figure 4 This is the differential scanning calorimetry test result of the glass in Example 1 of the present invention, with three heating-cooling cycles.

[0058] Figure 5 These are polarized photos of the glass in Example 1 of the present invention at different rotation angles.

[0059] Figure 6 : is the radiation luminescence spectrum of the glass scintillator screen of Example 1 of the present invention.

[0060] Figure 7 1 and 2 are imaging results of elbow joints with different bending angles using the flat glass scintillating screen of Example 1 of the present invention.

[0061] Figure 8 These are the imaging results of the elbow joints at different bending angles using the reconstructed glass scintillating screen of Example 1 of the present invention.

[0062] Fig. 9 The reconstructed glass scintillator screen of Example 1 of the present invention performs multi-angle co-forming imaging on a capsule having a distortion spring embedded therein.

[0063] Fig.10 This is the price comparison result of the raw materials of the glass scintillator screen of Example 1 of the present invention and the raw materials of the commercial scintillator. DETAILED DESCRIPTION

[0064] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0065] The present invention will be further described in detail below in conjunction with specific embodiments. It should be noted that the specific embodiments are intended to explain the present invention rather than to limit it.

[0066] Embodiment 1:

[0067] Using an organic-inorganic hybrid material (TPT) 2 MnB 4 (TPT = propyl triphenylphosphine bromide) realizes the reconfigurable preparation of glass scintillating screen and performs X-ray co-formation imaging, which specifically includes the following steps:

[0068] (1) Raw material weighing: In order to avoid the influence of impurities on the luminescence performance of the glass scintillator, high-purity monomer raw materials TPT and inorganic metal salt MnBr were purchased. 2 ·4H 2 O, the raw material purity is 99.99%. The organic raw material TPT and inorganic metal salt MnBr 2 ·4H 2O was weighed according to the stoichiometric ratio of 2:1, of which the organic component TPT was 6.16 g and the inorganic component MnBr 2 ·4H 2 O is 2.29g.

[0069] (2) Raw material pre-synthesis: weigh TPT and MnBr 2 ·4H 2 O was placed in an agate mortar for full grinding. In order to allow the two raw materials to react fully, the grinding time was maintained at 30 minutes. After grinding, it was taken out, and the color of the raw material turned light pink. When irradiated with ultraviolet light with a wavelength of 365nm, it can be seen that the reacted raw material emits green fluorescence, indicating that the two monomer raw materials have reacted.

[0070] (3) High-temperature melting of raw materials: After the fully ground raw materials are placed in silicone molds of different sizes, they are placed in a high-temperature oven for melting, and the temperature is set at 220±1°C. The raw materials are kept in the high-temperature oven for 15-20 minutes to ensure that the solid particles are completely transformed into melts and stabilized for several minutes.

[0071] (4) Molding of glass scintillating screen: The rectangular silicone mold with melt is taken out from the high temperature oven, and the temperature difference between the melting temperature and the room temperature is used as the driving force for quenching. After standing for several minutes, the mold is removed to obtain glass scintillating screens of different sizes, such as Figure 1 , Figure 2 As shown in (A), it can be seen that its surface is smooth and has good transparency.

[0072] (5) Reconstruction of glass scintillator: Glass scintillator screen has good thermal and chemical stability, and can be re-melted near the melting point to achieve the purpose of matching imaging objects of different shapes. The existing glass scintillator screen is re-melted to obtain glass scintillator screens of different shapes, such as Figure 3 As shown in B. Taking advantage of its glass transition temperature, the rectangular glass scintillation screen is placed at a specific temperature (55±1℃) for heating and softening, and can be reconstructed multiple times according to the required different shapes to achieve the purpose of matching imaging objects of different shapes. The rectangular glass scintillation screen is reconstructed according to toy balls of different diameters (6 cm to 9 cm) and magic rulers of different shapes, as shown in Figure 3 As shown in (D) and (E).

[0073] No one has yet conducted research on the Young's modulus and hardness of glass and crystals of the same composition at room temperature. Figure 2 The experimental results of (C) show that the hardness of glass is greater than that of crystal. This shows that glass has good rigidity, that is, after solidification at room temperature, it is not easy to undergo secondary deformation. Secondly, due to the glass transition temperature (Tg ) is 45°C. At a heating temperature higher than the glass transition temperature, the material will soften, which is very beneficial for the reconstruction of the glass. The present invention can fit the outer contour of objects with variable shapes to be conformal, thereby further realizing conformal X-ray imaging. Therefore, based on the above-mentioned purpose, the present invention tests the Young's modulus and hardness of glass at 55°C, once every five minutes, and a total of three tests. It shows that even under a smaller load of 100μN, the glass shows a greater indentation depth and its hardness is significantly reduced. And with the extension of the heat treatment time, the hardness continues to decrease. After 15 minutes, it drops to 0.00027GPa, which is 3 orders of magnitude lower than room temperature. It is extremely soft, indicating that it has a good deformable property, which is convenient for using the same glass screen to reconstruct different objects, which is conducive to realizing X-ray conformal imaging, such as Figure 2 As shown in (D). Figure 2 Figure (E) in the middle is a verification, where (1) at room temperature, a 100g weight was placed on the bent glass screen, and the glass screen did not break. (2) at 55°C, a 10g weight was placed on the glass screen, causing a significant deformation. (3)-(4) at 55°C, the softening characteristics were used to further manually bend the glass into different complex shapes.

[0074] The thermal properties of the rectangular glass scintillator obtained in Example 1 were tested. Its glass transition temperature was 41.4°C, crystallization point was 89.8°C, melting point was 132.7°C, and it could remain stable when heated to 260°C without decomposition, indicating that the glass had good stability. In the second and third scans, the glass state could be stable. The differential scanning calorimetry test results, such as Figure 4 shown.

[0075] Polarized light microscope observation of the rectangular glass scintillator screen obtained in Example 1 showed no polarization phenomenon, and the powder diffraction test showed no obvious crystal diffraction peak, indicating that the glass scintillator material was successfully obtained. Figure 2 Middle (B), Figure 5 shown.

[0076] The rectangular glass scintillator obtained in Example 1 was tested for radiation emission spectrum, and its emission wavelength was 536 nm, which matched the sensitive wavelength range of the detector. Figure 6 shown.

[0077] The rectangular glass scintillator in Example 1 is reconstructed to match elbow joints with different bending degrees and perform X-ray co-form imaging. It can be seen that compared with the blurred image produced by the flat-panel detector, the reconstructed glass scintillator can effectively shorten the distance between the irregular object and the imaging scintillator, thereby improving the imaging resolution and showing more structural details between the ulna, radius and humerus. The flat-panel glass scintillator images the elbow joints with different bending angles, such as Figure 7 As shown in the figure; the reconstructed scintillation screen images the elbow joint at different bending angles, such as Figure 8 shown.

[0078] The rectangular glass scintillator screen in Example 1 was melted and reconstructed to match the capsule containing the metal spring. The structural deformation inside the capsule was further revealed through imaging at different angles, such as Fig. 9 shown.

[0079] The price of the raw materials used in the rectangular glass scintillator screen in Example 1 is compared with the price of commercial scintillator raw materials. Fig.10 As shown, the raw material of the glass scintillating screen is low-priced, which provides favorable conditions for large-area preparation.

[0080] Embodiment 2:

[0081] An organic-inorganic composite glass scintillator material (3Br-TPT) 2 MnB 4 (3Br-TPT = (3-bromopropyl) triphenylphosphonium bromide) realizes the reconfigurable processing of the glass scintillating screen, and the steps are as described in Example 1, except that in step (1), the organic molecule selected is (3-bromopropyl) triphenylphosphonium bromide with a purity of 99.99%, of which 3Br-TPT is 4.64g, MnBr 2 ·4H 2 O is 1.43g. In step (3), in order to obtain a square glass scintillator, the selected silicone mold is square (2cm×2cm×2cm), and the high-temperature melting temperature is set to 200±1°C. The glass scintillator screen has good thermal and chemical stability, and can be re-melted near the melting point to achieve the purpose of matching imaging objects of different shapes. Taking advantage of its glass transition temperature, the glass scintillator screen is placed in an oven at a specific temperature for heating. After softening, it can be reconstructed multiple times according to the required different shapes to achieve the purpose of matching imaging objects of different shapes. Finally, X-ray coform imaging is performed.

[0082] Embodiment 3:

[0083] An organic-inorganic composite glass scintillator material (TPT) 2 ZnBr4 (TPT = (3-propyl) triphenylphosphine bromide) to achieve the reconfigurable processing of the glass scintillating screen, the steps are as described in Example 1, except that in step (1), the inorganic metal salt selected is ZnBr 2 , purity is 99.99%, of which the required organic raw material TPT is 6.164g, and the inorganic metal salt ZnBr 2 The glass scintillator is 1.80 g. In step (3), the high temperature melting temperature is set to 210 ± 1 ° C. The glass scintillator has good thermal and chemical stability, and can be re-melted near the melting point to achieve the purpose of matching imaging objects of different shapes. Taking advantage of its glass transition temperature, the glass scintillator is placed in an oven at a specific temperature for heating. After softening, it can be reconstructed multiple times according to the required different shapes to achieve the purpose of matching imaging objects of different shapes. Finally, X-ray co-forming imaging is performed.

[0084] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a reconfigurable glass scintillating screen, characterized in that: include: placing the organic-inorganic hybrid material in a mold to melt it, thereby obtaining a mold with a melt; The mold with the melt is quenched and demoulded to obtain a glass scintillating screen; The glass scintillator screen is heated to soften it, and then matched with the shape of the imaging object, and solidified and formed again to obtain; The organic component of the organic-inorganic hybrid material is an organic phosphine derivative or a guanidine derivative, the inorganic component is a metal halide salt, and the organic-inorganic hybrid material satisfies the conditions of glass transition temperature < crystallization temperature < melting point < decomposition point and glass transition temperature / melting point > 0.

67.

2. The method for preparing a reconfigurable glass scintillating screen according to claim 1, characterized in that: The organic-inorganic hybrid material is (TPT)2MnBr4, (3Br-TPT)2MnBr4 or (TPT)2ZnBr4; Or, the synthesis method of the organic-inorganic hybrid material: after uniformly mixing the organic raw material and the inorganic raw material, grinding them to obtain the organic-inorganic hybrid material; Preferably, the grinding time is 30 min-2 h, or the raw material is placed in a planetary ball mill for grinding, the swing frequency is set to 20-40 times / second, and the duration is maintained at 30 min-1 h; Alternatively, an organic solvent is added to the raw material, preferably at least one of n-hexane, cyclohexane, dichloromethane, chloroform, methanol, ethanol and acetone. Alternatively, after grinding, observe whether the color of the raw material changes or irradiate it with light of wavelengths of 365nm or 254nm to see whether the synthesized raw material emits fluorescence at a specific wavelength to verify whether the reaction is complete.

3. The method for preparing a reconfigurable glass scintillating screen according to claim 1, characterized in that: The mold is a square silicone mold, a circular silicone mold, a triangular silicone mold, a rhombus silicone mold, a trapezoidal silicone mold or a parallelogram silicone mold.

4. The method for preparing a reconfigurable glass scintillating screen according to claim 3, characterized in that: A square silicone mold with a side length of 1 cm to 25 cm, preferably 1±0.1 cm, 3±0.1 cm, 6±0.1 cm, 9±0.1 cm, 12±0.1 cm, 15±0.1 cm, 18±0.1 cm, 20±0.1 cm, 22±0.1 cm, 24±0.1 cm, 25±0.1 cm; Or, a rectangular silicone mold, the length of its long side is 5 cm to 45 cm, preferably, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm, 40±0.1 cm, 45±0.1 cm; the length of its short side is 1 cm to 35 cm, preferably, 1±0.1 cm, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm; Or, a circular silicone mold, the inner diameter of which is 2 cm to 35 cm, preferably, 2±0.1 cm, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm; Or, a triangular silicone mold, wherein the lengths of the three sides of the triangle are 5 cm to 35 cm, preferably, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm; Or, a diamond-shaped silicone mold, the side length of which is 5 cm to 35 cm, preferably, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm; Or, a trapezoidal silicone mold, the length of the upper base is 5 cm to 20 cm, 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, and the length of the lower base is 10 cm to 35 cm, preferably 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm; Or, a parallelogram-shaped silicone mold, wherein two parallel sides are 5 cm to 35 cm in length, preferably 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm, and the other two parallel sides are 5 cm to 35 cm in length, preferably 5±0.1 cm, 10±0.1 cm, 15±0.1 cm, 20±0.1 cm, 25±0.1 cm, 30±0.1 cm, 35±0.1 cm; Or, the wall thickness of the silicone mold is 0.1 cm to 0.5 cm, preferably, 0.1±0.05 cm, 0.15±0.05 cm, 0.2±0.05 cm, 0.25±0.05 cm, 0.3±0.05 cm, 0.35±0.05 cm, 0.4±0.05 cm, 0.45±0.05 cm, 0.5±0.05 cm; Or, the groove depth of the silicone mold is 0.5 cm to 5 cm, preferably, 0.5±0.05 cm, 1±0.05 cm, 1.5±0.05 cm, 2±0.05 cm, 3±0.05 cm, 4±0.05 cm.

5. The method for preparing a reconfigurable glass scintillating screen according to claim 1, characterized in that: The temperature setting range of the heating oven is 180°C-270°C, preferably 180±1°C, 190±1°C, 200±1°C, 210±1°C, 220±1°C, 230±1°C, 240±1°C, 250±1°C, 260±1°C, and 270±1°C.

6. The method for preparing a reconfigurable glass scintillating screen according to claim 1, characterized in that: The quenching treatment was performed at room temperature.

7. The method for preparing a reconfigurable glass scintillating screen according to claim 1, characterized in that: The reconstructed material is heated at ±10°C of the glass transition temperature.

8. The method for preparing a reconfigurable glass scintillating screen according to claim 1, characterized in that: The reshaped shape is constructed according to the imaged object, including various geometric shapes, preferably, a rectangle, a square, a circle, a trapezoid, a triangle, a rhombus, and a parallelogram; The bending angle of the reconstructed glass scintillator screen is 10° to 80°, preferably 10±1°, 20±1°, 30±1°, 40±1°, 50±1°, 60±1°, 70±1°, 80±1°.

9. A reconfigurable glass scintillating screen prepared by the method according to any one of claims 1 to 8.

10. Use of the reconfigurable glass scintillator screen according to claim 9 in X-ray coform imaging.

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