X-ray composite radiation shielding material and preparation method and application thereof

Abstract

The invention provides an X-ray composite radiation shielding material and a preparation method and application thereof, and belongs to the technical field of radiation protection. The photoelectric effect and the scattering effect of X-rays in the material are remarkably enhanced by using high atomic number elements contained in the metal oxide, so that the transmittance of the X-rays is effectively reduced. Meanwhile, the oxide material has good chemical stability and environmental friendliness, and the toxicity and aging problems caused by a traditional lead-based shielding material can be avoided. The prepared composite radiation shielding material has the advantages of being low in cost, light in weight, easy to process, good in flexibility, non-toxic, environmentally friendly and the like, the shielding efficiency of an X-ray shielding coating reaches up to 70% or above when the X-ray photon energy is 70 kV or below, and the generated secondary reflectance can be reduced by 35-80% compared with lead.

Description

Technical Field

[0001] This invention relates to the field of radiation protection technology, and in particular to an X-ray composite radiation shielding material, its preparation method, and its application. Background Technology

[0002] X-rays are electromagnetic waves with extremely high frequency, extremely short wavelength, and high energy, capable of penetrating various materials. As a common type of ionizing radiation, high-energy ionizing radiation, particularly X-rays, has been widely applied in fields such as medical imaging, nuclear energy facilities, industrial flaw detection, and aerospace with the development of modern science and technology and the socio-economic landscape. However, due to the high energy of X-rays, exposure to these high-energy and highly penetrating rays can pose potential harm to the human body. This is because high-energy ionizing radiation alters cellular molecules after acting on living organisms, causing damage. Therefore, to reduce the harm caused by ionizing radiation, effective radiation shielding materials are needed for protection.

[0003] Currently, commonly used traditional radiation shielding materials mainly include lead plates, lead glass, barium sulfate, and concrete. However, although these shielding materials have high radiation attenuation capabilities, they still have many limitations in practical applications, such as high processing difficulty, poor material uniformity, insufficient flexibility, easy cracking, limited durability, and potential toxicity, making it difficult to meet the development needs of lightweight and green environmental protection.

[0004] In recent years, composite radiation shielding materials based on polymers have gradually attracted attention. X-ray absorption can be achieved by introducing high atomic number inorganic fillers into a polymer matrix. However, the dispersion characteristics of different inorganic fillers and polymer matrices vary significantly, easily leading to uneven filler dispersion (agglomeration) and poor flexibility (powder particles floating on the surface), thus affecting the shielding performance and mechanical properties of the material. Simultaneously, some polymer matrix materials still have shortcomings in terms of environmental friendliness and sustainability. Therefore, a radiation shielding material that can ensure X-ray shielding performance while also possessing characteristics such as low cost, lightweight, easy processing, good flexibility, and non-toxicity is urgently needed, which has significant research and application value. Summary of the Invention

[0005] The purpose of this invention is to provide a composite radiation shielding material, its preparation method, and its application. By rationally combining inorganic metal oxide shielding materials with environmentally friendly polymer matrix materials, the overall performance and environmental friendliness of the material are improved while enhancing X-ray shielding performance.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing an X-ray composite radiation shielding material, comprising the following steps: A mixture is prepared by mixing a metal oxide with a polymer and a dispersing solvent. The mixture is deposited on a substrate and annealed to obtain an X-ray composite radiation shielding material.

[0007] Preferably, the metal oxide includes one or more of aluminum oxide, calcium oxide, zinc oxide, tin oxide, antimony oxide, barium oxide, tungsten oxide, bismuth oxide, lanthanum oxide, cerium oxide, europium oxide, and gadolinium oxide.

[0008] Preferably, the polymer comprises one or more of the following: thermoplastic vulcanizate (TPV), thermoplastic elastomer (TPE), sodium carboxymethyl cellulose (CMC), polymethyl methacrylate (PMMA), polyurethane (PU), thermoplastic polyurethane (TPU), polyvinyl alcohol (PVA), polyimide (PI), polyvinylpyrrolidone (PVP), ethylene-vinyl acetate copolymer (EVA), hydrogenated styrene-butadiene block copolymer (SEBS), polyvinylidene fluoride (PVDF), and polydimethylsiloxane (PDMS). The mass ratio of the polymer to the metal oxide is 1~11:4~10.

[0009] Preferably, the dispersing solvent includes one or more of water, methanol, ethanol, n-butanol, toluene, dimethyl sulfoxide, N,N-dimethylformamide, isopropanol, acetone, dichloromethane, and ethyl acetate; the ratio of the metal oxide to the dispersing solvent is 1g:5~20mL.

[0010] Preferably, the deposition method includes one or more of spin coating, blade coating, filler coating, and spray coating.

[0011] Preferably, the substrate comprises one or more of natural rubber, leather, glass, nonwoven fabric, woven fabric, and plastic.

[0012] Preferably, the annealing treatment is performed at a temperature of 40~120℃ for a time of 60~360min.

[0013] Preferably, after the annealing treatment, the thickness of the shielding coating formed on the substrate is 0.15~0.5mm.

[0014] The present invention provides an X-ray composite radiation shielding material prepared by the preparation method described in the above technical solution.

[0015] This invention provides the application of the X-ray composite radiation shielding material described in the above technical solution in X-ray shielding.

[0016] This invention provides a method for preparing an X-ray composite radiation shielding material. The method utilizes the high atomic number elements contained in metal oxides to significantly enhance the photoelectric and scattering effects of X-rays within the material, thereby effectively reducing X-ray transmittance. Simultaneously, oxide materials possess excellent chemical stability and environmental friendliness, avoiding the toxicity and aging problems associated with traditional lead-based shielding materials. This invention leverages a dispersing solvent to effectively transfer grinding energy, continuously breaking down metal oxide particles into smaller, non-granular powders, thus improving the dispersibility of inorganic fillers in the polymer matrix. The prepared composite radiation shielding material has a multi-oxide composite structure, with high atomic number metal oxide fillers dispersed within the polymer matrix, forming multiple phase interfaces within the material. This allows X-rays to be absorbed and scattered during propagation, thereby achieving effective attenuation of X-ray energy.

[0017] The composite radiation shielding material prepared by this invention has the advantages of low cost, lightweight, easy processing, good flexibility, non-toxicity and environmental protection. Moreover, the shielding efficiency of the X-ray shielding coating is as high as 70% or more when the X-ray photon energy is below 70kV. The secondary reflection ratio can be reduced by 35-80% compared with lead, and it is also lighter than lead. Attached Figure Description

[0018] Figure 1 This is a flowchart illustrating the preparation process of the X-ray composite radiation shielding material of the present invention. Figure 2 Metallographic micrograph of the PI film with shielding coating obtained in Example 1; Figure 3 To theoretically calculate the linear absorption coefficients of different materials (Bi2O3, Gd2O3, WO3, Pb) for X-rays of different energies; Figure 4 The shielding efficiencies of Bi2O3-WO3 (a) with a mass ratio of 7:3 in Example 1, Bi2O3-Gd2O3 (b) with a mass ratio of 7:3 in Example 2, and Bi2O3-Gd2O3-WO3 (c) with a mass ratio of 4:3:3 in Example 3 are given. Figure 5 The shielding efficiency of Bi2O3, Gd2O3 and WO3 in the mass ratio of 4:3:3 in Example 4; Figure 6 The backscattering ratio of Bi2O3, Gd2O3 and WO3 in the mass ratio of 4:3:3 in Example 4 (compared to Pb). Figure 7 The backscattering ratio (compared to Pb) of Bi2O3, Gd2O3 and WO3 in the mass ratio of 4:3:3 in Example 5. Detailed Implementation

[0019] In this invention, unless otherwise specified, the raw materials or reagents required for preparation are all commercially available products well known to those skilled in the art.

[0020] like Figure 1 As shown, this invention provides a method for preparing an X-ray composite radiation shielding material, comprising the following steps: A mixture is prepared by mixing a metal oxide with a polymer and a dispersing solvent. The mixture is deposited on a substrate and annealed to obtain an X-ray composite radiation shielding material.

[0021] In this invention, the metal oxide preferably includes one or more of aluminum oxide, calcium oxide, zinc oxide, tin oxide, antimony oxide, barium oxide, tungsten oxide, bismuth oxide, lanthanum oxide, cerium oxide, europium oxide, and gadolinium oxide, more preferably bismuth oxide and tungsten oxide in a mass ratio of 7:3, or bismuth oxide and gadolinium oxide in a mass ratio of 7:3, or bismuth oxide, gadolinium oxide, and tungsten oxide in a mass ratio of 4:3:3.

[0022] In this invention, the polymer preferably includes one or more of the following: thermoplastic vulcanizate (TPV), thermoplastic elastomer (TPE), sodium carboxymethyl cellulose (CMC), polymethyl methacrylate (PMMA), polyurethane (PU), thermoplastic polyurethane (TPU), polyvinyl alcohol (PVA), polyimide (PI), polyvinylpyrrolidone (PVP), ethylene-vinyl acetate copolymer (EVA), hydrogenated styrene-butadiene block copolymer (SEBS), polyvinylidene fluoride (PVDF), and polydimethylsiloxane (PDMS). When the polymer is two or more of the above, this invention does not have a special limitation on the ratio of different types of polymers, and any ratio is acceptable. This invention does not have a special limitation on the source and specific type of the polymer; commercially available products well known in the art are acceptable.

[0023] In this invention, the polymer is preferably used in the form of a polymer solution or in the form of commercially available A and B adhesives; the concentration of the polymer solution is preferably 0.075~0.2 g / mL, more preferably 0.1~0.125 g / mL. This invention does not impose any particular limitation on the type of solvent used in the polymer solution; any conventional solvent known in the art capable of dissolving the aforementioned polymer is acceptable; in the embodiments of this invention, toluene, DMF, or water are specifically used.

[0024] In this invention, the mass ratio of the polymer to the metal oxide is preferably 1~11:4~10, more preferably 1.5~11:5~10, and even more preferably 2~4:5~8.

[0025] In this invention, the dispersing solvent preferably includes one or more of deionized water, methanol, ethanol, n-butanol, toluene, dimethyl sulfoxide, N,N-dimethylformamide, isopropanol, acetone, dichloromethane, and ethyl acetate; when the dispersing solvent is two or more of the above, this invention does not have a special limitation on the ratio of different types of dispersing solvents, and any ratio is acceptable.

[0026] In this invention, the preferred ratio of the metal oxide to the dispersing solvent is 1g:5~20mL, more preferably 1g:10~15mL.

[0027] In this invention, the metal oxide is preferably mixed with a dispersing solvent and then ground to ensure uniform dispersion of the metal oxide. The resulting mixture is then filtered, and the filtered powder is placed on a hot plate for drying (to promote rapid evaporation of the dispersing solvent; the drying temperature is preferably 40~60℃). After drying, the resulting mixed metal oxide powder is added to a polymer. This invention does not impose any special limitations on the filtration, drying, and grinding processes; they can be performed according to procedures well known in the art.

[0028] In this invention, the deposition method preferably includes one or more of spin coating, blade coating, filler coating and spray coating. This invention does not impose any special limitations on the specific operating conditions of the deposition method, and can be carried out in accordance with methods well known in the art.

[0029] In this invention, the substrate preferably comprises one or more of natural rubber, leather, glass, nonwoven fabric, woven fabric, and plastic, and more preferably a polyimide (PI) film. This invention does not impose any special limitations on the specific specifications and source of the substrate; commercially available products well-known in the art can be used.

[0030] In this invention, the annealing temperature is preferably 40~120℃, more preferably 50~80℃, and the time is preferably 60~360min, more preferably 120~240min, and even more preferably 180min. This invention achieves drying by evaporating the solvent through annealing.

[0031] In this invention, after the annealing treatment, the thickness of the shielding coating formed on the substrate is preferably 0.15~0.5mm, more preferably 0.2~0.35mm, and even more preferably 0.25~0.3mm.

[0032] The present invention provides an X-ray composite radiation shielding material prepared by the preparation method described in the above technical solution.

[0033] This invention provides the application of the X-ray composite radiation shielding material described in the above technical solution in X-ray shielding.

[0034] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0035] Unless otherwise specified, the experimental methods described in the various embodiments of this invention are conventional methods; unless otherwise specified, the reagents and raw materials described below are all commercially available.

[0036] Example 1

[0037] 1.5 g of polymer SEBS was added to 20 mL of toluene and completely dissolved at room temperature to obtain a polymer solution with a concentration of 0.075 g / mL. Grind and mix 5g of Bi2O3 and WO3 in a mass ratio of 7:3 with 50mL of ethanol. Filter the mixture and dry the powder obtained by filtration on a hot plate at 50°C. Add the resulting mixed metal oxide powder to the polymer solution and continue to stir evenly at room temperature to obtain a mixed solution. A polyimide (PI) base film was fixed on a glass plate, and then a mixture was applied to the PI film and coated to ensure that the mixture was evenly deposited on the PI base film. The entire mixture was then placed in a 50°C oven for annealing for 180 minutes to obtain an X-ray composite radiation shielding material with a shielding coating thickness of 0.2 mm.

[0038] Figure 2 Metallographic micrograph of the PI film with a shielding coating obtained in Example 1; as shown Figure 2 As shown, the shielding coating prepared in Example 1 is uniformly dispersed and free of agglomeration.

[0039] Example 2

[0040] 1.5 g of polymer SEBS was added to 20 mL of toluene and completely dissolved at room temperature to obtain a polymer solution with a concentration of 0.075 g / mL. Grind and mix 5g of Bi2O3 and Gd2O3 in a mass ratio of 7:3 with 50mL of ethanol. Filter the mixture and dry the powder obtained by filtration on a hot plate at 50℃. Add the resulting mixed metal oxide powder to the polymer solution and continue stirring until homogeneous to obtain a mixed solution. A polyimide (PI) base film was fixed on a glass plate, and then a mixture was applied to the PI film and coated by scraping to ensure that the mixture was evenly deposited on the PI base film. The entire mixture was then placed in an oven at 50°C for annealing for 180 minutes to obtain an X-ray shielding coating with a thickness of 0.2 mm.

[0041] The shielding coating prepared in Example 2 was uniformly dispersed and free of agglomeration.

[0042] Example 3

[0043] 1.5 g of polymer SEBS was added to 20 mL of toluene and completely dissolved at room temperature to obtain a polymer solution with a concentration of 0.075 g / mL. Grind and mix 5g of Bi2O3, Gd2O3 and WO3 in a mass ratio of 4:3:3 with 50mL of ethanol. Filter the mixture and dry the powder obtained by filtration on a hot plate at 50℃. Add the resulting mixed metal oxide powder to the polymer solution and continue stirring until homogeneous to obtain a mixed solution. A polyimide (PI) base film was fixed on a glass plate, and then a mixture was applied to the PI film and coated by scraping to ensure that the mixture was evenly deposited on the PI base film. The entire mixture was then placed in an oven at 50°C for annealing for 180 minutes to obtain an X-ray shielding coating with a thickness of 0.2 mm.

[0044] The shielding coating prepared in Example 3 was uniformly dispersed and free of agglomeration.

[0045] Figure 3 To theoretically calculate the linear absorption coefficients of different materials (Bi2O3, Gd2O3, WO3, Pb) for X-rays of different energies, the absorption degree at different X-ray photon energies was calculated and compared with lead.

[0046] Figure 4 The shielding efficiencies of Bi2O3-WO3 (a) with a mass ratio of 7:3 in Example 1, Bi2O3-Gd2O3 (b) with a mass ratio of 7:3 in Example 2, and Bi2O3-Gd2O3-WO3 (c) with a mass ratio of 4:3:3 in Example 3 are described; Figure 3 As shown, under X-ray photon irradiation of 20~70kV, the shielding efficiency of the shielding coating obtained in Example 1 reaches 93~82%, the shielding efficiency of the shielding coating obtained in Example 2 reaches 95~84%, and the shielding efficiency of the shielding coating obtained in Example 3 reaches 96~85%.

[0047] Example 4

[0048] 2g of polymer SEBS was added to 20mL of toluene and completely dissolved at room temperature to obtain a polymer solution with a concentration of 0.1 g / mL. Grind and mix 5g of Bi2O3, Gd2O3 and WO3 in a mass ratio of 4:3:3 with 50mL of ethanol. Filter the mixture and dry the powder obtained by filtration on a hot plate at 50℃. Add the resulting mixed metal oxide powder to the polymer solution and continue to stir until homogeneous to obtain a mixed solution. A polyimide (PI) base film was fixed on a glass plate, and then a mixture was applied to the PI film and coated by scraping to ensure that the mixture was uniformly deposited on the PI base film. The entire mixture was then placed in an oven at 50°C for annealing for 240 minutes to obtain an X-ray shielding coating with a thickness of 0.35 mm.

[0049] Figure 5 The shielding efficiency of Bi2O3, Gd2O3 and WO3 in the mass ratio of 4:3:3 in Example 4; Figure 6 The backscattering ratio (compared to Pb) of Bi₂O₃, Gd₂O₃, and WO₃ in the mass ratio of 4:3:3 in Example 4; the shielding coating prepared in Example 4 is uniformly dispersed and has advantages such as good flexibility, resistance to cracking, and durability. Figures 5-6 It is known that under X-ray photon irradiation with energies of 20-70 kV, the shielding efficiency of this shielding coating reaches 99-89%, and the backscattering is reduced by more than 35% compared to Pb, especially at 40-60°, where it can be reduced by more than 50%.

[0050] Example 5

[0051] 11g of PDMS polymer A and B (mass ratio of A to B 10:1) were poured into a beaker and stirred for 1 hour to obtain a homogeneous mixed solution, which was denoted as the polymer solution. 5g of Bi2O3, Gd2O3 and WO3 in a mass ratio of 4:3:3 after dispersion were ground and mixed with 50mL of ethanol. The resulting mixture was filtered, and the powder obtained by filtration was placed on a hot plate and dried at 50℃. The resulting mixed metal oxide powder was added to the polymer solution and stirred until homogeneous to obtain a mixed solution. A polyimide (PI) base film was fixed on a glass plate, and then a mixture was applied to the PI film and coated by scraping to ensure that the mixture was uniformly deposited on the PI base film. The entire mixture was then placed in an oven at 80°C for annealing for 240 minutes to obtain an X-ray shielding coating with a thickness of 0.3 mm.

[0052] The shielding coating prepared in Example 5 exhibits advantages such as uniform dispersion, good flexibility, resistance to cracking, and durability. Under X-ray photon irradiation at 20–70 kV, the shielding efficiency reaches 92–78%. Figure 7 The backscattering ratio (compared to Pb) of Bi₂O₃, Gd₂O₃, and WO₃ in the mass ratio of 4:3:3 in Example 5 is as follows: Figure 7 As shown, backscattering is reduced by more than 40% compared to Pb, especially at 40~60° where it can be reduced by more than 50%.

[0053] Example 6

[0054] 2.5 g of PVDF polymer was added to 20 mL of DMF and completely dissolved at room temperature to obtain a polymer solution with a concentration of 0.125 g / mL. Grind and mix 5g of Bi2O3, Gd2O3 and WO3 in a mass ratio of 4:3:3 with 50mL of ethanol. Filter the mixture and dry the powder obtained by filtration on a hot plate at 50℃. Add the resulting mixed metal oxide powder to the polymer solution and continue to stir until homogeneous to obtain a mixed solution. A polyimide (PI) base film was fixed on a glass plate, and then a mixture was applied to the PI film and coated by scraping to ensure that the mixture was evenly deposited on the PI base film. The entire mixture was then placed in an oven at 50°C for annealing for 240 minutes to obtain an X-ray shielding coating with a thickness of 0.3 mm.

[0055] The shielding coating prepared in Example 6 exhibits advantages such as uniform dispersion, good flexibility, resistance to cracking, and durability. Furthermore, under X-ray photon irradiation at 20-70 kV, the shielding efficiency reaches 98-89%, and the backscattering is reduced by more than 35% compared to Pb, especially at 40-60° where it can be reduced by more than 50%.

[0056] Example 7

[0057] Add 4g of PVA polymer to 20mL of deionized water. After complete dissolution at room temperature, a polymer solution with a concentration of 0.2 g / mL is obtained. Grind and mix 5g of Bi2O3, Gd2O3 and WO3 in a mass ratio of 4:3:3 with 50mL of ethanol. Filter the mixture and dry the powder obtained by filtration on a hot plate at 50℃. Add the resulting mixed metal oxide powder to the polymer solution and continue to stir until homogeneous to obtain a mixed solution. A polyimide (PI) base film was fixed on a glass plate, and then a mixture was applied to the PI film and coated by scraping to ensure that the mixture was uniformly deposited on the PI base film. The entire mixture was then placed in an oven at 50°C for annealing for 180 minutes to obtain an X-ray shielding coating with a thickness of 0.25 mm.

[0058] The shielding coating prepared in Example 7 exhibits advantages such as uniform dispersion, good flexibility, resistance to cracking, and durability. Furthermore, under X-ray photon irradiation at 20-70 kV, the shielding efficiency reaches 98-89%, and the backscattering is reduced by more than 45% compared to Pb, especially at 40-60° where it can be reduced by more than 50%.

[0059] 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 composite radiation shielding material, characterized in that, Includes the following steps: A mixture is prepared by mixing a metal oxide with a polymer and a dispersing solvent. The mixture is deposited on a substrate and annealed to obtain an X-ray composite radiation shielding material.

2. The preparation method according to claim 1, characterized in that, The metal oxides include one or more of aluminum oxide, calcium oxide, zinc oxide, tin oxide, antimony oxide, barium oxide, tungsten oxide, bismuth oxide, lanthanum oxide, cerium oxide, europium oxide, and gadolinium oxide.

3. The preparation method according to claim 1 or 2, characterized in that, The polymers include one or more of the following: thermoplastic vulcanized rubber, thermoplastic elastomer, sodium carboxymethyl cellulose, polymethyl methacrylate, polyurethane, thermoplastic polyurethane, polyvinyl alcohol, polyimide, polyvinylpyrrolidone, ethylene-vinyl acetate copolymer, hydrogenated styrene-butadiene block copolymer, polyvinylidene fluoride, and polydimethylsiloxane. The mass ratio of the polymer to the metal oxide is 1~11:4~10.

4. The preparation method according to claim 1 or 2, characterized in that, The dispersing solvent includes one or more of water, methanol, ethanol, n-butanol, toluene, dimethyl sulfoxide, N,N-dimethylformamide, isopropanol, acetone, dichloromethane, and ethyl acetate; the ratio of the metal oxide to the dispersing solvent is 1g:5~20mL.

5. The preparation method according to claim 1, characterized in that, The deposition method includes one or more of spin coating, blade coating, filler coating, and spray coating.

6. The preparation method according to claim 1 or 5, characterized in that, The substrate includes one or more of natural rubber, leather, glass, nonwoven fabric, woven fabric, and plastic.

7. The preparation method according to claim 1, characterized in that, The annealing process is performed at a temperature of 40~120℃ for a time of 60~360min.

8. The preparation method according to claim 1 or 7, characterized in that, After the annealing treatment, the thickness of the shielding coating formed on the substrate is 0.15~0.5mm.

9. The X-ray composite radiation shielding material prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the X-ray composite radiation shielding material according to claim 9 in X-ray shielding.

Images