Preparation method of a reconfigurable glass scintillating screen and its application in X-ray coform imaging

Abstract

The present invention provides a method for preparing a reconfigurable glass scintillator screen and its application in X-ray conformal imaging, belonging to the field of X-ray imaging technology, and specifically comprising the following steps: raw material pre-synthesis, high-temperature melting, glass scintillator screen molding, and reconfiguration processing. The present invention effectively solves the problems of high difficulty in processing commercial scintillators in flat-panel X-ray detectors, non-plasticity of shape, and inability to achieve conformality with irregularly shaped objects to be measured, while overcoming the problems of light scattering and decreased transmittance in conventional doped polymer flexible scintillator screens. The morphology of the glass scintillator screen involved in the present invention can give full play to its reconfigurable characteristics and be processed according to the morphology of the object to be measured, thereby further completing conformal X-ray imaging under the condition of constantly changing object shapes, effectively solving the imaging distortion problem caused by non-conformality, and having high imaging resolution.

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 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 those 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, X-ray-based radiation detection is one of the key technologies, and its application range covers from industrial testing to clinical diagnosis. X-ray detectors are an important part of the X-ray radiation detection system, 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 (Bi4Ge3O 12 ), yttrium lutetium silicate ((Lu, Y)2SiO5) 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 conducting industrial inspections of 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, a three-dimensional image of the object can be constructed. However, the increase in radiation dose caused by multiple X-ray exposures is a concern, especially when X-rays are used to detect lesions in the human body. Taking all factors into consideration, X-ray coform imaging provides the best solution to the above problems. In X-ray coform imaging, the imaging detector closely fits the geometric contours of the object to be inspected, which can effectively solve the problem of image distortion 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, which is 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 screens have shown certain advantages in X-ray curved surface imaging. However, the above-mentioned flexible scintillating screens also have 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] To overcome the above problems, glass materials with high transparency and uniformity have become advantageous candidates. Typically, inorganic scintillating glass is prepared by high-temperature sintering (greater than 1000°C), which requires relatively harsh experimental conditions. In contrast, organic-inorganic hybrid scintillating glass prepared under mild conditions (around 200°C) has more advantages. At the same time, organic-inorganic hybrid glass contains large organic components, which makes it less likely to crystallize during high-temperature quenching. Therefore, it has attracted great attention from researchers. For example, organic-inorganic hybrid scintillating glass has been prepared using divalent manganese combined with organophosphine derivatives or guanidine derivatives, monovalent copper combined with organophosphine derivatives, and trivalent antimony (Sb(III)) combined with organophosphine derivatives, 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 flat-plate types. Researchers have also attempted to make it into curved scintillating screens for non-planar X-ray imaging. "Organic–Inorganic Hybrid Mn-Based Transparent Glass for Curved X-Ray Scintillation Imaging" discloses a plastic perovskite glass scintillator, but it requires molds and specialized extrusion molding to make curved screens. 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. Reconfigurable scintillating screens for X-ray coform imaging in different or changing application scenarios have not yet been explored. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention provides a method for preparing a reconfigurable glass scintillator screen and its application in X-ray coform imaging. This method leverages the low glass transition temperature and excellent chemical and thermal stability of organic-inorganic hybrid scintillator glass to enable reconfigurable processing to match irregularly shaped objects and achieve high-resolution X-ray coform imaging. This method overcomes the difficulties of processing commercial scintillators, the primary functional layer of X-ray flat-panel detectors, and the difficulty of achieving reconfigurable processing to accommodate diverse imaging needs for more refined imaging. Furthermore, conventional doped flexible scintillator screens suffer from uneven scintillator light intensity, light scattering, and low transmittance.

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

[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 and melting it to obtain a mold with a melt;

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

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

[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)2MnBr4, (3Br-TPT)2MnBr4 or (TPT)2ZnBr4, 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 reconfigurable properties.

[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 the organic-inorganic hybrid material;

[0016] Preferably, the grinding time is 30 min-2 h, or the raw materials are placed in a planetary ball mill for grinding, with the rocking frequency set at 20-40 times / second and the duration 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 if its color changes or is irradiated with light of wavelengths of 365 nm or 254 nm to see if 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-shaped 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, and 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, and 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, or 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 base 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 base 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, the parallelogram-shaped silicone mold has two parallel sides with a 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, or 35 ± 0.1 cm, and the other two parallel sides have a 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, or 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, or 4±0.05 cm.

[0030] In some embodiments, the oven temperature is set in the range of 180°C to 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, or 270±1°C. If bubbles are present in the melt, they can be gently agitated or the oven can be evacuated to remove them. This prevents bubbles from solidifying within the glass during the quenching process, causing light scattering and reducing X-ray imaging quality. Furthermore, care should be taken during demolding to prevent the glass scintillator from breaking.

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

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

[0033] Utilizing the glass scintillator's excellent thermal and chemical stability, it can be remolded near its melting point to match the shape of the imaging object. In some embodiments, the remolded shape is constructed based on the imaging object and includes various geometric shapes, preferably rectangles, squares, circles, trapezoids, triangles, rhombuses, and parallelograms.

[0034] Utilizing the glass transition temperature (GTT) of the glass scintillator screen, the screen can be repeatedly reconstructed into various shapes near the GTT, depending on the desired object being imaged. The shapes and specifications are not limited to those described below. In some embodiments, the reconstructed glass scintillator screen has a curvature angle of 10° to 80°, preferably 10±1°, 20±1°, 30±1°, 40±1°, 50±1°, 60±1°, 70±1°, or 80±1°. A rectangular glass scintillator screen can also be bent and bonded to the object being imaged, with the specific curvature determined by the object being imaged.

[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 scintillating screen, it is necessary to purchase high-purity monomer raw materials or purify the commercial monomer raw materials multiple times by solution method, gas phase method, and zone melting method. Subsequently, the organic components and inorganic components used are weighed according to a certain stoichiometric ratio. The stoichiometric ratio of the organic component to the inorganic component 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 inert atmosphere to avoid stoichiometric imbalance and deviation in the raw material synthesis.

[0037] (2) Pre-synthesis of raw materials: Place the weighed raw materials with a specific ratio in an agate mortar and grind them thoroughly. In order to allow the two raw materials to react fully, the grinding time is maintained at 30 minutes to 2 hours. Alternatively, place the raw materials in a planetary ball mill and grind them with a swing frequency set at 20-40 times / second, and the duration is maintained between 30 minutes and 1 hour. In addition, in order to ensure sufficient contact between the raw materials, a small amount of volatile organic solvents such as n-hexane, cyclohexane, dichloromethane, chloroform, methanol, ethanol, acetone, etc. can be added. 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, which can be used 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 material from oxidative decomposition due to excessive temperature. 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) Molding of the glass scintillator screen: After the melt is stabilized, it is removed from the high-temperature oven and quenched using the large temperature difference between the melting point and the room temperature. Do not touch or shake it manually during the cooling process. After a few minutes, a glass scintillator screen with a certain shape is obtained.

[0040] (5) Reconstruction processing of glass scintillating screen: Taking advantage of its good thermal stability and chemical stability, it can be re-melted and reshaped to match imaging objects of different shapes, or taking advantage of its glass transition temperature, it can be placed in an oven at a specific temperature for heating. The temperature setting should be near the glass transition temperature. After softening after a few minutes, it can be repeatedly processed in multiple cycles according to the required different shapes to match imaging objects of different shapes.

[0041] (6) X-ray coform imaging of glass scintillating screen: An X-ray coform imaging system was built using a commercial X-ray source, an imaging object, a reconstructed glass scintillating 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, a guanidine derivative, etc.

[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 below the melting point of the material. The temperature used for zone melting purification should be 10-50°C above 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 application of the above-mentioned reconfigurable glass scintillating screen in X-ray coform imaging.

[0048] Beneficial effects of the present 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 leverages the excellent thermal and chemical stability and low glass transition temperature of glass materials to achieve reconstructive processing of glass scintillating screens. This effectively overcomes the drawbacks of using flat-panel detectors, achieving the goal of X-ray co-form imaging of irregularly shaped objects, and further meeting the needs of refined imaging.

[0051] (3) The present invention uses a glass scintillating screen for X-ray co-form 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, which constitute a part of the present invention, are used to provide a further understanding of the present invention. 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 scintillation screen prepared using a rectangular silicone mold in Example 1 of the present invention.

[0055] Figure 2The characterization of rectangular glass scintillators 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) Diffraction patterns of (TPT)2MnBr4 crystals, glass powders and simulated powder diffraction patterns of (TPT)2MnBr4. The inset shows (TPT)2MnBr4 crystals grown using the antisolvent diffusion method. (C) Load-displacement curves of (TPT)2MnBr4 glass and crystals at room temperature and 55°C. Six cyclic tests were performed at room temperature with a load of 5000μN; three cyclic tests were performed at 55°C on (TPT)2MnBr4 glass with a load of 100μN and a test time interval of 5 minutes. (D) A magnified image of the results of three cyclic tests on (TPT)2MnBr4 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 was manually bent into different complex shapes at 55°C (3)-(4).

[0056] Figure 3 The following is a diagram of the reconstructed processing of Example 1 of the present invention: (A) Schematic diagram of the remelting and shaping process of (TPT)2MnBr4 glass at 220°C. (B) Schematic diagram of the remelting and shaping of (TPT)2MnBr4 glass into different shapes. (C) Schematic diagram of the conformal processing of (TPT)2MnBr4 glass at 55°C. (D) Schematic diagram of (TPT)2MnBr4 glass heated at 55°C and conformed to toy balls of different diameters (6 cm to 9 cm). The top photo shows the conformal formation of a glass scintillating screen and toy balls, and the bottom photo shows the corresponding reconstructed glass. (E) Schematic diagram of the conformal formation of (TPT)2MnBr4 glass heated at 55°C and conformed to different shapes of magic rulers. The top photo shows the conformal formation of a glass scintillating screen and magic rulers, and the bottom photo shows the corresponding reconstructed glass.

[0057] Figure 4 These are the differential scanning calorimetry test results for the glass of 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 radiant luminescence spectrum of the glass scintillating screen of Example 1 of the present invention.

[0060] Figure 7 These are the imaging results of elbow joints at 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 elbow joints at different bending angles using the reconstructed glass scintillating screen of Example 1 of the present invention.

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

[0063] Figure 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 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 with reference to specific embodiments. It should be noted that the specific embodiments are intended to explain the present invention rather than to limit it.

[0066] Example 1:

[0067] An organic-inorganic hybrid material (TPT) 2MnBr4 (TPT = propyltriphenylphosphonium bromide) is used to realize the reconfigurable preparation of glass scintillating screen and perform X-ray co-formation imaging, which specifically includes the following steps:

[0068] (1) Raw material weighing: To prevent the influence of impurities on the luminescent properties of the glass scintillating screen, high-purity monomer raw materials TPT and inorganic metal salt MnBr2·4H2O were purchased with a raw material purity of 99.99%. The organic raw material TPT and inorganic metal salt MnBr2·4H2O were weighed according to the stoichiometric ratio of 2:1, with the organic component TPT being 6.16 g and the inorganic component MnBr2·4H2O being 2.29 g.

[0069] (2) Raw material presynthesis: Weighed TPT and MnBr2·4H2O were placed in an agate mortar and ground thoroughly. To ensure a complete reaction between the two raw materials, the grinding time was maintained at 30 minutes. After grinding, the raw material was removed from the mortar. The color of the raw material turned light pink. Irradiation with ultraviolet light at a wavelength of 365 nm revealed green fluorescence from the reacted raw material, indicating that the two monomer raw materials had 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 at a temperature of 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 a melt and stabilized for several minutes.

[0071] (4) Molding of glass scintillating screen: Take out the rectangular silicone mold with melt from the high temperature oven, use the temperature difference between melting temperature and room temperature as the driving force to quench it, let it stand for a few minutes, and then demould it 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: 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. The existing glass scintillator is re-melted to obtain glass scintillator of different shapes, such as Figure 3 As shown in B. Taking advantage of its glass transition temperature, the rectangular glass scintillating screen is heated and softened at a specific temperature (55±1℃), and can be reconstructed multiple times according to the required shapes to achieve the purpose of matching imaging objects of different shapes. The rectangular glass scintillating screen is reconstructed according to toy balls of different diameters (6 cm to 9 cm) and magic rulers of different shapes, as shown in the figure. 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 with 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, it is not easy to undergo secondary deformation after solidification at room temperature. Secondly, due to the glass transition temperature (T g ) 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 contours of objects with variable shapes and perform conformal conformal conformal conformal imaging, 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, indicating that even under a smaller load of 100μN, the glass shows a larger indentation depth and its hardness is significantly reduced. Moreover, as the heat treatment time increases, the hardness continues to decrease. After 15 minutes, it drops to 0.00027GPa, which is 3 orders of magnitude lower than that at room temperature. It is extremely soft, indicating that it has a good deformable property, which facilitates the use of the same glass screen to reconstruct different objects, which is beneficial to the realization of X-ray conformal imaging, such as Figure 2 As shown in (D). Figure 2Figure (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 significant deformation. (3)-(4) At 55°C, the softening properties were utilized to further manually bend the glass into different complex shapes.

[0074] Thermal properties of the rectangular glass scintillating screen obtained in Example 1 were tested. The glass transition temperature was 41.4°C, the crystallization point was 89.8°C, and the melting point was 132.7°C. It remained stable when heated to 260°C without decomposition, indicating that the glass had good stability. In addition, the glass state was stable in the second and third scans. The differential scanning calorimetry test results are as follows: Figure 4 shown.

[0075] Polarizing 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 glassy 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 was reconstructed to match elbow joints with different degrees of bending and perform X-ray coform 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 irregular objects 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 can image 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, as shown in the figure. Figure 8 shown.

[0078] The rectangular glass scintillating 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 by imaging at different angles, such as Figure 9 shown.

[0079] The prices of the raw materials used in the rectangular glass scintillator screen in Example 1 are compared with those of commercial scintillator raw materials. Figure 10 As shown, the raw materials of the glass scintillating screen are low-priced, which provides favorable conditions for large-scale preparation.

[0080] Example 2:

[0081] A method for reconfigurable processing of a glass scintillator screen using an organic-inorganic composite glass scintillator material (3Br-TPT)2MnBr4 (3Br-TPT = (3-bromopropyl)triphenylphosphine bromide) is described. The steps are as described in Example 1, except that in step (1), the organic molecule selected is (3-bromopropyl)triphenylphosphine bromide with a purity of 99.99%, of which 3Br-TPT is 4.64g and MnBr2·4H2O is 1.43g. In step (3), to obtain a square glass scintillator, a square silicone mold (2cm×2cm×2cm) is selected, 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 its melting point to achieve the purpose of matching imaging objects of different shapes. Taking advantage of its glass transition temperature, the glass scintillator is heated in an oven at a specific temperature. Once softened, it can be reshaped multiple times to match the desired shape of the imaging object. Finally, X-ray co-formation imaging is performed.

[0082] Example 3:

[0083] A method for reconfigurable processing of a glass scintillator screen using an organic-inorganic composite glass scintillator material (TPT) 2ZnBr4 (TPT = (3-propyl) triphenylphosphine bromide) is described in Example 1, except that in step (1), the inorganic metal salt selected is ZnBr2 with a purity of 99.99%, wherein the required organic raw material TPT is 6.164g and the inorganic metal salt ZnBr2 is 1.80g. In step (3), the high-temperature melting temperature is set to 210±1°C. The glass scintillator screen has good thermal and chemical stability and can be remolded 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 reconfigured multiple times according to the desired different shapes to achieve the purpose of matching imaging objects of different shapes. Finally, X-ray co-formation imaging is performed.

[0084] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection 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 and melting it to obtain a mold with a melt; The mold with the melt is quenched and demoulded to obtain a glass scintillating screen; The glass scintillating screen is heated to soften it, then matched to the shape of the imaging object, and solidified again to obtain a film; 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, 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; The organic-inorganic hybrid material is (TPT)2MnBr4, (3Br-TPT)2MnBr4 or (TPT)2ZnBr4; In (TPT)2MnBr4, TPT is propyltriphenylphosphonium bromide; In (3Br-TPT)2MnBr4, 3Br-TPT is (3-bromopropyl)triphenylphosphonium bromide; In (TPT)2ZnBr4, TPT is (3-propyl)triphenylphosphonium bromide.

2. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: The synthesis method of the organic-inorganic hybrid material comprises the following steps: uniformly mixing an organic raw material and an inorganic raw material, and then grinding the mixture to obtain the organic-inorganic hybrid material.

3. The method for preparing a reconfigurable glass scintillating screen according to claim 2, wherein: The grinding time is 30 min-2 h, or the raw materials are placed in a planetary ball mill for grinding, with the rocking frequency set at 20-40 times / second and the duration maintained at 30 min-1 h; Alternatively, an organic solvent is added to the raw material, wherein the organic solvent is selected from 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 365 nm or 254 nm to see whether the synthesized raw material emits fluorescence at a specific wavelength to verify whether the reaction is complete.

4. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: 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.

5. The method for preparing a reconfigurable glass scintillating screen according to claim 4, wherein: A square silicone mold with a side length selected from one of the following ranges: 1 cm to 25 cm, 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, wherein the length of its long side is selected from one of the following ranges: 5 cm to 45 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, 40±0.1 cm, 45±0.1 cm; the length of its short side is selected from one of the following ranges: 1 cm to 35 cm, 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, whose inner diameter is selected from one of the following ranges: 2 cm to 35 cm, 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 selected from one of the following ranges: 5 cm to 35 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 diamond-shaped silicone mold, wherein the side length of the diamond is selected from one of the following ranges: 5 cm to 35 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 trapezoidal silicone mold, wherein the length of the upper base side is selected from one of the following ranges: 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 side is selected from one of the following ranges: 10 cm to 35 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 parallelogram-shaped silicone mold, wherein the lengths of two parallel sides are selected from one of the following ranges: 5 cm to 35 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, and the lengths of the other two parallel sides are selected from one of the following ranges: 5 cm to 35 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, the wall thickness of the silicone mold is selected from one of the following ranges: 0.1 cm to 0.5 cm, 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; Alternatively, the groove depth of the silicone mold is selected from one of the following ranges: 0.5 cm to 5 cm, 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.

6. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: The temperature setting range of the heating oven is 180℃-270℃.

7. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: The temperature of the heating oven is 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 or 270±1°C.

8. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: The quenching treatment was performed at room temperature.

9. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: Reconstruction processing is performed by heating at a temperature within ±10°C of the glass transition temperature.

10. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: The reshaped shapes are constructed based on the imaged object and include various geometric shapes.

11. The method for preparing a reconfigurable glass scintillating screen according to claim 10, wherein: The geometric shape is a rectangle, a square, a circle, a trapezoid, a triangle, a rhombus or a parallelogram.

12. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: The bending angle of the reconstructed glass scintillator screen is 10° to 80°.

13. The method for preparing a reconfigurable glass scintillating screen according to claim 1, wherein: The bending angle of the reconstructed glass scintillating screen is 10±1°, 20±1°, 30±1°, 40±1°, 50±1°, 60±1°, 70±1° or 80±1°.

14. A reconfigurable glass scintillating screen prepared by the method according to any one of claims 1 to 13.

15. Use of the reconfigurable glass scintillating screen according to claim 14 in X-ray coform imaging.

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