Preparation method of X-ray shielding coating
An X-ray shielding coating was prepared by combining Bi-based perovskite with polymers, which solved the problems of large weight, poor flexibility and severe backscattering of existing shielding coatings. It achieved lightweight, uniform and efficient shielding effect, and is suitable for radiation protection equipment.
Patent Information
- Application Number
- CN202511617652.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-06
- Publication Date
- 2026-01-09
AI Technical Summary
Existing X-ray shielding coatings are heavy, lack flexibility, and suffer from severe backscattering, making it difficult to meet the requirements for lightweight, flexible, and easy-to-process materials.
An X-ray shielding coating was prepared by combining Bi-based perovskite materials with polymers through a process of dissolution, deposition, and annealing, thereby optimizing its dispersibility and backscattering performance.
The prepared X-ray shielding coating is lightweight, uniform, and has excellent mechanical properties. It reduces backscattering by more than 50%, is suitable for complex environments, and is inexpensive, making it suitable for radiation protection equipment.
Smart Images
Figure CN121293830A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of shielding coating technology, and more particularly to a method for preparing an X-ray shielding coating. Background Technology
[0002] X-rays, as high-energy electromagnetic radiation with strong penetrating power, are widely used in medical diagnosis, industrial flaw detection, and security inspection. With the continuous expansion of application scenarios, radiation protection for operators and precision instruments is becoming increasingly prominent. Therefore, developing efficient X-ray radiation shielding coatings is key to solving these problems. Traditional shielding materials (such as Pb, nano-metal oxide derivatives, etc.) have excellent shielding performance, but generally suffer from drawbacks such as heavy weight and poor film flexibility, making it difficult to meet the lightweight, flexible, and easy-to-process requirements of scenarios such as medical protective clothing and complex surface protection for high-precision instruments. To overcome these problems, the research community has developed various composite shielding materials based on polymers (such as polyethylene, epoxy resin, etc.). These materials are not only lightweight and easy to mold, but their shielding performance can also be improved by incorporating nano-metal oxides. However, existing composite shielding materials often struggle to simultaneously achieve both lightweight and high efficiency. For example, to achieve efficient shielding, high-density nanoparticles are usually required, which are prone to aggregation and sedimentation during preparation, resulting in poor dispersibility and insufficient uniformity, affecting the reliability of the shielding coating. In contrast, perovskite materials with high Z-elements, with their rich structures and excellent physicochemical properties, are ideal choices for high-performance shielding coatings. In particular, Bi-based perovskite coatings can theoretically not only effectively absorb X-rays, preventing transmission damage and backscattered radiation damage, but also interact with special groups such as -COOH and -OH in polymers through coordination and bonding, achieving uniform dispersion and high loading. Based on this background, this invention, through the selection of Bi-based perovskites and polymers, develops a radiation shielding coating that is lightweight, efficient, mechanically strong, and environmentally friendly, effectively addressing the severe backscattering problem of shielding materials such as lead, and meeting the growing demand for radiation protection. Summary of the Invention
[0003] The purpose of this invention is to provide a method for preparing an X-ray shielding coating, so as to solve the problems of large weight, poor film flexibility, and severe backscattering in the prior art of X-ray shielding coatings.
[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing an X-ray shielding coating, comprising the following steps: (1) Dissolve polymer A in organic solvent B to obtain solution I; (2) Dissolve Bi-based perovskite material C in organic solvent D to obtain solution II; (3) Deposit solution I and solution II sequentially onto the substrate, and then anneal them; (4) Repeat step (3) to obtain the X-ray shielding coating.
[0005] Preferably, in step (1), the polymer A comprises one or more of polymethyl methacrylate, polyvinyl alcohol, polystyrene, polyimide, polyurethane, polyethylene, polypropylene, polylactic acid and silicone rubber; and the organic solvent B comprises one or more of toluene, n-hexane, n-octane, dimethyl sulfoxide, N,N-dimethylformamide, ethanol and isopropanol.
[0006] Preferably, in step (1), the concentration of polymer A in solution I is 50~200 mg / mL.
[0007] Preferably, in step (2), the Bi-based perovskite material C is a three-dimensional material or a low-dimensional material.
[0008] Preferably, the Bi-based perovskite material C comprises A3Bi2X9, A2AgBiX6, ABiX4, and A4MnBi2X. 12 One or more of the following, wherein A is one or more of Cs, Rb, MA, organic amines and organophosphorus, and X is a halogen or pseudohalogen.
[0009] Preferably, in step (2), the organic solvent D contains one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; and the concentration of Bi-based perovskite material C in solution II is 0.05~1.00 mol / L.
[0010] Preferably, in step (3), the material of the substrate includes glass, plastic, metal, natural leather or fibrous fabric.
[0011] Preferably, the substrate is treated with a plasma cleaner for 3-5 minutes.
[0012] Preferably, in step (3), the annealing temperature is 110~130℃ and the annealing time is 400~500min.
[0013] Preferably, in step (4), the repetition is repeated 2 to 8 times.
[0014] The beneficial effects of this invention are: The X-ray shielding coating prepared by this invention can achieve a shielding efficiency (thickness less than 100 micrometers) of over 20% for single-layer X-ray shielding coatings when the X-ray photon energy is below 100 keV. The backscattering ratio is reduced by more than 50% compared to Pb, especially reaching over 80% at angles of 60° to 90°.
[0015] The X-ray shielding coating prepared by this invention has advantages such as high efficiency, lightweight, uniform dispersion, flexibility, low cost, environmental friendliness, and applicability to various complex environments. It can be used for medical ionizing radiation protection, personal and mobile protective equipment, and other applications in radiation-hazardous locations. Attached Figure Description
[0016] Figure 1 EDX image of the X-ray shielding coating prepared in Example 1; Figure 2 The image shows the test results of the adhesion strength between the X-ray shielding coating prepared in Example 2 and the substrate. Figure 3 The stability test results of the single layer of X-ray shielding coating prepared in Example 3 after bending 0, 50, and 500 times are shown. Figure 4 The single-layer X-ray shielding coating prepared in Example 4 was tested at a tube voltage of 70 kV. p (W target) X-ray shielding efficiency stability test diagram; Figure 5 This is a comparison image showing the backscattering of the X-ray shielding coating prepared in Example 5 and the lead shielding coating. Figure 6 The diagram shows the shielding efficiency of the single-layer X-ray shielding coating prepared in Example 6. Detailed Implementation
[0017] This invention provides a method for preparing an X-ray shielding coating, comprising the following steps: (1) Dissolve polymer A in organic solvent B to obtain solution I; (2) Dissolve Bi-based perovskite material C in organic solvent D to obtain solution II; (3) Deposit solution I and solution II sequentially onto the substrate, and then anneal them; (4) Repeat step (3) to obtain the X-ray shielding coating.
[0018] In this invention, in step (1), the polymer A comprises one or more of polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polystyrene (PS), polyimide (PI), polyurethane (PU), polyethylene (PE), polypropylene (PP), polylactic acid (PLA), and silicone rubber (SR); the organic solvent B comprises one or more of toluene, n-hexane, n-octane, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), ethanol, and isopropanol.
[0019] In this invention, in step (1), the concentration of polymer A in solution I is 50~200 mg / mL, specifically 50 mg / mL, 80 mg / mL, 100 mg / mL, 150 mg / mL, or 200 mg / mL.
[0020] In this invention, in step (2), the Bi-based perovskite material C is a three-dimensional material or a low-dimensional material.
[0021] In this invention, the Bi-based perovskite material C comprises A3Bi2X9, A2AgBiX6, ABiX4, and A4MnBi2X. 12 One or more of the following, wherein A is one or more of Cs, Rb, MA, organic amines and organophosphorus, and X is a halogen or pseudohalogen.
[0022] In this invention, the pseudohalogenated compound comprises PF6, BF4, or SCN.
[0023] In this invention, in step (2), the organic solvent D contains one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the concentration of Bi-based perovskite material C in solution II is 0.05~1.00 mol / L, specifically 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L and 0.8 mol / L.
[0024] In this invention, the dissolution of Bi-based perovskite material C in organic solvent D is preferably carried out by heating, wherein the heating temperature is 70~90℃, preferably 80℃.
[0025] In this invention, in step (3), the material of the substrate includes glass, plastic, metal, natural leather or fibrous fabric.
[0026] In this invention, the substrate is treated with a plasma cleaner for 3-5 minutes.
[0027] In this invention, in step (3), the deposition method can be spraying, spin coating or scraping.
[0028] In this invention, in step (3), it is preferable to dry the solution I deposited on the substrate before depositing solution II.
[0029] In this invention, the volume ratio of solution I to solution II during each deposition is 3~20:3~10.
[0030] In this invention, in step (3), the annealing temperature is 110~130℃, preferably 115~125℃, and more preferably 120℃, and the annealing time is 400~500min, specifically 420min, 440min, 460min, 480min, and 500min.
[0031] In this invention, in step (4), the number of repetitions is 2 to 8 times, specifically 3, 5, 7, or 8.
[0032] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0033] Example 1
[0034] PMMA and organic solvent DMF were mixed and heated to 60°C. After complete dissolution, a transparent solution was obtained, denoted as Solution I, with a concentration of 200 mg / mL. MA3Bi2Br9 was dissolved in the organic solvent DMF, heated to 80℃, stirred at 500 rpm for 5 h, and filtered to obtain a transparent solution, which was designated as solution II with a concentration of 0.3 mol / L. Glass substrate (size 4) The glass substrate was treated with a plasma cleaner for 4 minutes (8 cm), and then solution I (3 mL) was spin-coated onto the glass substrate at 3000 rpm to ensure uniform coverage of the polymer. The substrate was then dried in a vacuum drying oven at 60°C for 300 minutes. Solution II (10 mL) was sprayed onto a substrate containing polymer, and then annealed in a vacuum drying oven at 120 °C for 500 min to allow the solvent to evaporate completely, forming a 65 μm thick single-layer X-ray shielding coating; the above steps were repeated 5 times to obtain the X-ray shielding coating.
[0035] from Figure 1 As can be seen, the X-ray shielding coating prepared in Example 1 is uniformly distributed, dense, and free of agglomeration and pores. The single-layer X-ray shielding coating achieves an attenuation efficiency of 20.5% for X-ray photon energies of 40 keV.
[0036] Example 2
[0037] PU and organic solvent DMF were mixed and heated to 80°C. After complete dissolution, a transparent solution was obtained, denoted as Solution I, with a concentration of 50 mg / mL. Cs3Bi2Br9 was dissolved in a mixed solvent of DMF and DMSO (the volume ratio of DMF to DMSO was 9:1), heated to 80°C, stirred at 500 rpm for 5 h, and filtered to obtain a transparent solution, which was designated as solution II with a concentration of 0.4 mol / L. aluminum sheet (size 4) 8cm) was treated with a plasma cleaner for 5 minutes, then solution I (20mL) was sprayed onto the aluminum sheet, and then dried in a vacuum drying oven at 60℃ for 300 minutes to allow the solvent to completely evaporate and the polymer to be evenly covered. Solution II (10 mL) was sprayed onto a substrate containing polymer, and then annealed in a vacuum drying oven at 120°C for 500 min to allow the solvent to evaporate completely. The above steps were repeated 7 times to obtain an X-ray shielding coating.
[0038] from Figure 2 It can be seen that the X-ray shielding coating prepared in Example 2 is tightly integrated with the aluminum substrate, and there is no gap between the film and the substrate.
[0039] The X-ray shielding coating prepared in Example 2 reduced the backscattering ratio by more than 53% on average compared to Pb when the X-ray photon energy was 40 keV, especially reaching more than 70% at angles of 60° to 90°.
[0040] Example 3
[0041] PMMA, PU (mass ratio 3:1) and organic solvent DMSO were mixed and heated to 60°C. After complete dissolution, a transparent solution was obtained, denoted as Solution I, with a concentration of 80 mg / mL. Rb3Bi2I9 was dissolved in DMSO, heated to 80℃, stirred at 500 rpm for 5 h, and filtered to obtain a transparent solution, which was designated as solution II with a concentration of 0.3 mol / L. Fiber fabric (size 4) 8cm) was treated with a plasma cleaner for 5 minutes, then solution I (20mL) was sprayed onto the fiber fabric, and then dried in a vacuum drying oven at 60℃ for 300 minutes to allow the solvent to evaporate completely and the polymer to be evenly covered. Solution II (10 mL) was sprayed onto a substrate containing polymer, and then annealed in a vacuum drying oven at 120°C for 500 min to allow the solvent to evaporate completely. The above steps were repeated 5 times to obtain an X-ray shielding coating.
[0042] The X-ray shielding coating prepared in Example 3 is tightly integrated with the fiber fabric, exhibiting excellent flexibility and mechanical properties. Figure 3 It can be seen that the X-ray shielding coating can withstand 500 cycles of aging without significant performance degradation.
[0043] Example 4
[0044] PVA and organic solvent DMF were mixed and heated to 60°C. After complete dissolution, a transparent solution was obtained, which was denoted as Solution I, with a concentration of 100 mg / mL. Cs2AgBiBr6 was dissolved in a mixed solvent of acetone and DMSO (volume ratio 4:1), heated to 80℃, stirred at 500 rpm for 5 h, and filtered to obtain a transparent solution, which was designated as solution II with a concentration of 0.5 mol / L. Plastic substrate (size 4) 8cm) was treated with a plasma cleaner for 3 minutes, then solution I (20mL) was sprayed onto the plastic substrate, and then dried in a vacuum drying oven at 60℃ for 300 minutes to allow the solvent to evaporate completely and the polymer to be evenly covered. Solution II (10 mL) was sprayed onto a substrate containing polymer, and then annealed in a vacuum drying oven at 120°C for 500 min to allow the solvent to evaporate completely, forming a single-layer X-ray shielding coating; the above steps were repeated 8 times to obtain the X-ray shielding coating.
[0045] from Figure 4 It can be seen that the single-layer X-ray shielding coating prepared in Example 4 has strong X-ray stability and its performance decays by less than 5% when the cumulative dose of continuous irradiation at X-ray photon energy of 70 keV exceeds 200 Gyair.
[0046] Example 5
[0047] PMMA, PU (mass ratio 6:1) and organic solvent DMF were mixed and heated to 60°C. After complete dissolution, a transparent solution was obtained, denoted as Solution I, with a concentration of 200 mg / mL. (PEA)3Bi2I9 was dissolved in the organic solvent DMF, heated to 80°C, stirred at 500 rpm for 5 h, and filtered to obtain a transparent solution, which was designated as solution II with a concentration of 0.2 mol / L. Plastic substrate (size 4) 8cm) was treated with a plasma cleaner for 3 minutes, and then solution I (3mL) was scraped onto the plastic substrate and dried in a vacuum drying oven at 60°C for 300 minutes to allow the solvent to evaporate completely and the polymer to be evenly covered. Solution II (5 mL) was scraped onto the substrate containing the polymer and then annealed in a vacuum drying oven at 120°C for 500 min to allow the solvent to evaporate completely. The above steps were repeated 3 times to obtain the X-ray shielding coating.
[0048] from Figure 5 It can be seen that the attenuation efficiency of the X-ray shielding coating prepared in Example 5 is more than 50% lower than that of Pb at a photon energy of 60 keV, especially at an angle of 60°~90°, where it can reach more than 80%.
[0049] Example 6
[0050] PP and the organic solvent isopropanol were mixed and heated to 60°C. After complete dissolution, a transparent solution was obtained, which was denoted as Solution I, with a concentration of 200 mg / mL. (PEA)3Bi2(PF6)9 was dissolved in N-methylpyrrolidone, heated to 80°C, stirred at 500 rpm for 5 h, and filtered to obtain a transparent solution, which was designated as solution II with a concentration of 0.8 mol / L. Fiber fabric substrate (size 4) 8cm) was treated with a plasma cleaner for 3 minutes, and then solution I (5mL) was scraped onto the fiber fabric substrate and dried in a vacuum drying oven at 60°C for 300 minutes to allow the solvent to evaporate completely and the polymer to be evenly covered. Solution II (3 mL) was coated onto a substrate containing polymer and then annealed in a vacuum drying oven at 120 °C for 500 min to allow the solvent to evaporate completely, resulting in a single-layer X-ray shielding coating with a thickness of 58 μm. The above steps were repeated 5 times to obtain the X-ray shielding coating.
[0051] The performance of the single-layer X-ray shielding coating in Example 6 was tested, and the results are as follows: Figure 6 As shown. From Figure 6 It can be seen that a single-layer X-ray shielding coating (thickness: 58μm) can achieve a shielding efficiency of over 20% at photon energies below 70 keV.
[0052] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing an X-ray shielding coating, characterized in that, Includes the following steps: (1) Dissolve polymer A in organic solvent B to obtain solution I; (2) Dissolve Bi-based perovskite material C in organic solvent D to obtain solution II; (3) Deposit solution I and solution II sequentially onto the substrate, and then anneal them; (4) Repeat step (3) to obtain the X-ray shielding coating.
2. The method for preparing the X-ray shielding coating according to claim 1, characterized in that, In step (1), the polymer A comprises one or more of polymethyl methacrylate, polyvinyl alcohol, polystyrene, polyimide, polyurethane, polyethylene, polypropylene, polylactic acid and silicone rubber; the organic solvent B comprises one or more of toluene, n-hexane, n-octane, dimethyl sulfoxide, N,N-dimethylformamide, ethanol and isopropanol.
3. The method for preparing the X-ray shielding coating according to claim 1 or 2, characterized in that, In step (1), the concentration of polymer A in solution I is 50~200 mg / mL.
4. The method for preparing the X-ray shielding coating according to claim 3, characterized in that, In step (2), the Bi-based perovskite material C is a three-dimensional material or a low-dimensional material.
5. The method for preparing the X-ray shielding coating according to claim 4, characterized in that, The Bi-based perovskite material C comprises A3Bi2X9, A2AgBiX6, ABiX4, and A4MnBi2X. 12 One or more of the following, wherein A is one or more of Cs, Rb, MA, organic amines and organophosphorus, and X is a halogen or pseudohalogen.
6. The method for preparing the X-ray shielding coating according to claim 2, 4, or 5, characterized in that, In step (2), the organic solvent D contains one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; the concentration of Bi-based perovskite material C in solution II is 0.05~1.00 mol / L.
7. The method for preparing the X-ray shielding coating according to claim 6, characterized in that, In step (3), the material of the substrate includes glass, plastic, metal, natural leather or fiber fabric.
8. The method for preparing the X-ray shielding coating according to claim 7, characterized in that, The substrate is treated with a plasma cleaner for 3-5 minutes.
9. The method for preparing the X-ray shielding coating according to claim 5, 7, or 8, characterized in that, In step (3), the annealing temperature is 110~130℃ and the annealing time is 400~500min.
10. The method for preparing the X-ray shielding coating according to claim 9, characterized in that, In step (4), the repetition is performed 2 to 8 times.