Thermoplastic manganese halide scintillation glass for curved surface X-ray imaging and preparation method thereof

Abstract

The invention belongs to the technical field of photoelectric materials and preparation thereof, and discloses thermoplastic manganese halide scintillation glass for curved surface X-ray imaging and a preparation method thereof, the material of the scintillation glass is organic-inorganic metal manganese halide, the structural general formula of the scintillation glass is # imgabs0 #, in which R is methyl, ethyl, n-propyl, n-butyl, n-amyl or n-hexyl; x is Cl, Br or I; the prepared scintillation glass can be softened after being heated within the temperature range of 45-55 DEG C due to the low glass-transition temperature, so that the scintillation glass can be bent and attached to the surface of an irregular object, and meanwhile, good transparency and light emitting uniformity are kept; in addition, after being customized and attached to an irregular object, the imaging material can recover to an initial plane shape through a simple flattening process, and can be repeatedly customized and formed to adapt to various irregular imaging objects, and the excellent customization plasticity and reusability of the imaging material are fully shown.

Description

Technical Field

[0001] The invention belongs to the technical field of optoelectronic materials and preparation thereof, and specifically relates to a method for preparing a flexible, highly transparent thermoplastic zero-dimensional manganese halide scintillating glass, and an application of the glass in curved surface X-ray imaging. Background Art

[0002] Scintillators are materials that emit light after absorbing high-energy particles such as X-rays. Despite the continuous development of X-ray detection technology, scintillator-based X-ray detectors have dominated the market in recent decades and have been widely used in non-destructive testing, medical imaging, and security inspections. However, with the growing demand for imaging objects with irregular geometries, the development of innovative flexible X-ray detectors has become particularly important. However, this is beyond the capabilities of current inorganic scintillators. In this context, metal halides have shown great advantages among the new generation of X-ray scintillating materials due to their diverse crystal structures and excellent luminescence properties.

[0003] To date, metal halide scintillators have been developed in the form of single crystals and polymer-halide composite films. Single crystals have shown significant advantages in achieving high imaging resolution due to their excellent optical uniformity and effective avoidance of light scattering. However, single crystal scintillators face problems of mechanical rigidity and extremely harsh growth conditions, which greatly hinder their practical applications, especially in the field of curved surface X-ray imaging. In contrast, polymer-halide composite films give scintillator materials good flexibility by embedding metal halide powders into a polymer matrix. Nevertheless, the composite films are usually opaque, and light scattering becomes an inherent disadvantage of such flexible composite films. Therefore, the current priority is to develop a scintillator material that combines efficient radioluminescence, low light scattering and high flexibility.

[0004] Recently, highly transparent thermoplastic metal halide scintillating glass has emerged as an emerging scintillating material, making curved X-ray imaging possible. However, the reports on thermoplastic scintillating glass are scarce, which severely limits the further development of this type of material. At the same time, the practical benefits and advantages of the reusability and customizability of thermoplastic scintillating glass have not been fully verified and studied. Summary of the invention

[0005] The purpose of the present invention is to solve the deficiencies in the prior art and to provide a thermoplastic manganese halide scintillating glass for curved surface X-ray imaging and a preparation method thereof.

[0006] In order to achieve the above object, the present invention is achieved through the following technical solutions:

[0007] In a first aspect, the present invention provides a thermoplastic manganese halide scintillating glass for curved surface X-ray imaging, which has reusability and plasticity, and can be softened by heating at a temperature of 45-55° C. The material of the manganese halide scintillating glass is an organic-inorganic metal manganese halide, and the general structural formula of the organic-inorganic metal manganese halide is as follows:

[0008]

[0009] Wherein R is methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl; X=Cl, Br, I.

[0010] Preferably, the organic-inorganic metal manganese halide is prepared by a one-pot method, and the synthesis route is as follows:

[0011]

[0012] Preferably, the preparation method of the organic-inorganic metal manganese halide is as follows:

[0013] The derivative ligand of triethylenediamine and manganese halide tetrahydrate are added into a reaction bottle at a molar ratio of 2:1, and 5-20 mL of a mixed solution of dichloromethane and ethanol are added, and the mixture is stirred sufficiently to obtain a clear solution. After the solution evaporates, an organic-inorganic metal manganese halide is obtained.

[0014] Preferably, the volume ratio of dichloromethane to ethanol is 2:1-5:1.

[0015] Preferably, the method comprises the following steps:

[0016] Step S1, fully grinding the organic-inorganic metal manganese halide into fine powder and filling the mold, then placing the mold on a heating table and continuously heating it in an air atmosphere to obtain a uniform high-temperature solution;

[0017] Step S2, annealing the high temperature solution obtained in step 1) to rapidly cool it to room temperature to obtain manganese halide scintillating glass.

[0018] Preferably, in step S1, the heating temperature is 180-250° C. and the heating time is 30-60 min.

[0019] In a second aspect, the present invention provides applications of the thermoplastic manganese halide scintillating glass for curved surface X-ray imaging in medical imaging, security inspection, and high energy physics.

[0020] The present invention has the following beneficial effects: (1) The present invention discloses a thermoplastic manganese halide scintillating glass and a preparation method thereof, wherein the glass has the characteristics of being customizable and reusable, and the scintillating glass is easy to prepare and can be produced and applied on a large scale.

[0021] (2) The thermoplastic scintillating glass prepared by the present invention has high transparency and excellent scintillating performance.

[0022] (3) The thermoplastic scintillating glass prepared in the present invention has a low glass transition temperature and can be softened by heating it within a temperature range of 45-55°C, which enables it to be easily bent and adhered to the surface of irregular objects while maintaining good transparency and luminous uniformity, thereby achieving high-quality curved surface X-ray imaging.

[0023] (4) After the thermoplastic scintillating glass prepared by the present invention is customized and attached to an irregular object, it can be easily restored to a flat state through a simple flattening process, and can then be repeatedly customized and molded to adapt to various irregular imaging objects, demonstrating its excellent customization plasticity and reusability. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the crystal structure of manganese halide (he-ted) 2MnBr4 prepared in Example 1 of the present invention;

[0025] Figure 2 This is a flow chart of the preparation of the thermoplastic manganese halide scintillating glass prepared in Example 2 of the present invention;

[0026] Figure 3 A physical picture of the thermoplastic manganese halide scintillating glass prepared in Example 2 of the present invention and a luminescent photo under ultraviolet light;

[0027] Figure 4 The normalized excitation-emission spectrum of the thermoplastic manganese halide scintillating glass prepared in Example 2 of the present invention;

[0028] Figure 5 The X-ray response spectrum of the thermoplastic manganese halide scintillating glass prepared in Example 2 of the present invention;

[0029] Figure 6 This is a transmittance spectrum of the thermoplastic manganese halide scintillating glass prepared in Example 2 of the present invention;

[0030] Figure 7 This is a curved surface imaging diagram of the thermoplastic manganese halide scintillating glass prepared in Example 2 of the present invention;

[0031] Figure 8 Schematic diagram of the reusable thermoplastic manganese halide scintillating glass prepared in Example 2 of the present invention. DETAILED DESCRIPTION

[0032] The present invention will be further described below in conjunction with the embodiments, but they are not intended to limit the present invention.

[0033] Example 1: Synthesis of organic-inorganic hybrid manganese halide

[0034] The synthetic route is as follows:

[0035]

[0036] Synthesis steps:

[0037] According to the molar ratio, the organic ligand and manganese bromide tetrahydrate are added to the reaction bottle in a ratio of 2:1, and 5-20mL of dichloromethane and ethanol solution (volume ratio of 2:1-5:1) are added, and stirred thoroughly to obtain a clear solution. The solution evaporates, and green crystals are obtained after three days.

[0038] Figure 1 Schematic diagram of the single crystal structure of the organic-inorganic hybrid manganese halide described in Example 1 (for simplicity, hydrogen atoms have been omitted).

[0039] The single crystal structure was measured using a single crystal X-ray diffractometer (Bruker D8 Quest).

[0040] Example 2: Preparation of thermoplastic manganese halide scintillating glass

[0041] The specific steps are as follows:

[0042] 1) Grind the organic-inorganic metal manganese halide structure 4 into fine powder and fill it in a mold. Then place the mold on a heating table at 180° C. and heat it in an air atmosphere for 30 minutes to obtain a uniform high-temperature solution;

[0043] 2) The mold containing the melt in step 1) is quickly taken off the heating table for annealing, and the mold is quickly cooled to room temperature to obtain a manganese halide scintillating glass.

[0044] Example 3: Preparation of thermoplastic manganese halide scintillating glass

[0045] The specific steps are as follows:

[0046] 1) Grind the organic-inorganic metal manganese halide structure 4 into fine powder and fill it in a mold. Then place the mold on a heating table at 200° C. and heat it in an air atmosphere for 40 minutes to obtain a uniform high-temperature solution;

[0047] 2) The mold containing the melt in step 1) is quickly taken off the heating table for annealing, and the mold is quickly cooled to room temperature to obtain a manganese halide scintillating glass.

[0048] Example 4: Preparation of thermoplastic manganese halide scintillating glass

[0049] The specific steps are as follows:

[0050] 1) Grind the organic-inorganic metal manganese halide structure 4 into fine powder and fill it in a mold. Then place the mold on a heating table at 250° C. and heat it in an air atmosphere for 60 minutes to obtain a uniform high-temperature solution;

[0051] 2) The mold containing the melt in step 1) is quickly taken off the heating table for annealing, and the mold is quickly cooled to room temperature to obtain a manganese halide scintillating glass.

[0052] Experimental Example 1: Test of Normalized Excitation Emission Spectrum of Thermoplastic Scintillation Glass

[0053] The excitation emission measurements were performed on an Edinburgh FLS-980 spectrophotometer using a 450W xenon lamp. The excitation spectrum ranged from 250nm to 500nm, and the emission spectrum ranged from 400nm to 750nm. The test results are shown in Figure 2. Figure 4 As shown, the emission peak of the scintillating glass is located at 520 nm, which is green light.

[0054] Experimental Example 2: Testing of X-ray Response Spectra of Thermoplastic Scintillating Glass

[0055] The X-ray response spectrum was measured on an Edinburgh FLS-980 spectrophotometer. The measured radiation intensity was 0.224 mGy air s -1 to 4.5 mGy air s -1 , the test results are as follows Figure 5 As shown, when the scintillating glass is irradiated by X-rays, its radiation luminescence intensity has a good linear response to the X-ray dose rate.

[0056] Experimental Example 3: Testing of the light transmittance spectrum of thermoplastic scintillating glass

[0057] The transmittance spectrum was measured on a Shimadzu UV-2600 spectrophotometer with an absorption wavelength range of 300nm–800nm. The test results are shown in Figure 6 As shown, the scintillating glass has a light transmittance of 80% in the visible light range, and the surface of the scintillating glass has high transparency.

[0058] Experimental Example 4: Application of Thermoplastic Scintillation Glass in Curved Surface X-ray Imaging

[0059] Thermoplastic scintillating glass has a low glass transition temperature and only needs to be heated to 45°C to achieve a softened state, which allows it to be easily bent and fitted onto the surface of irregular objects while maintaining good transparency and luminous uniformity. Figure 7As shown in the figure, the curved thermoplastic scintillating glass can be perfectly attached to the curved surface of the bookmark, while there is a clear separation between the flat scintillating screen and the bookmark. Therefore, the flat scintillating screen presents a blurry X-ray imaging picture of the bookmark, while in contrast, the curved scintillating glass can obtain a clear structural outline of the bookmark.

[0060] Experimental Example 5: Reusable properties of thermoplastic scintillating glass

[0061] After the thermoplastic scintillating glass is custom-attached to an irregular object, it can be restored to its original planar shape through a simple flattening process, and then can be custom-molded repeatedly to adapt to various irregular imaging objects. Figure 8 As shown, after the thermoplastic scintillator is attached to the surface of the prism, it can restore its original planar shape through a hot pressing process, and then can be continuously attached to the surfaces of the cylinder, pyramid and cone without any damage, demonstrating its excellent customizability and reusability.

[0062] The above shows and describes the basic principles, main features and advantages of the present invention. However, the above is only a specific embodiment of the present invention, and the technical features of the present invention are not limited thereto. Any other implementation methods derived by any technician in the field without departing from the technical solution of the present invention should be included in the patent scope of the present invention.

Claims

1. A thermoplastic manganese halide scintillating glass for curved surface X-ray imaging, characterized in that: It has reusability and plasticity, and can be softened by heating at 45-55°C. The material of the manganese halide scintillating glass is organic-inorganic metal manganese halide, and the general structural formula of the organic-inorganic metal manganese halide is as follows: Wherein R is methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl; X=Cl, Br, I.

2. The thermoplastic manganese halide scintillating glass for curved surface X-ray imaging according to claim 1, characterized in that: The organic-inorganic metal manganese halide is prepared by a one-pot method, and the synthesis route is as follows:

3. The thermoplastic manganese halide scintillating glass for curved surface X-ray imaging according to claim 2, characterized in that: The preparation method of the organic-inorganic metal manganese halide is specifically as follows: The derivative ligand of triethylenediamine and manganese halide tetrahydrate are added into a reaction bottle at a molar ratio of 2:1, and 5-20 mL of a mixed solution of dichloromethane and ethanol are added, and the mixture is stirred sufficiently to obtain a clear solution. After the solution evaporates, an organic-inorganic metal manganese halide is obtained.

4. The thermoplastic manganese halide scintillating glass for curved surface X-ray imaging according to claim 3, characterized in that: The volume ratio of the dichloromethane to the ethanol is 2:1-5:

1.

5. The method for preparing the thermoplastic manganese halide scintillating glass for curved surface X-ray imaging according to claim 1, characterized in that: The method comprises the following steps: Step S1, fully grinding the organic-inorganic metal manganese halide into fine powder and filling the mold, then placing the mold on a heating table and continuously heating it in an air atmosphere to obtain a uniform high-temperature solution; Step S2, annealing the high temperature solution obtained in step 1) to rapidly cool it to room temperature to obtain manganese halide scintillating glass.

6. The method for preparing thermoplastic manganese halide scintillating glass for curved surface X-ray imaging according to claim 4, characterized in that: In step S1, the heating temperature is 180-250° C. and the heating time is 30-60 min.

7. Application of the thermoplastic manganese halide scintillating glass for curved surface X-ray imaging according to claim 1 in medical imaging, security inspection and high energy physics.

Images