Composite functional materials supported on gadolinium, bismuth and boron, their preparation methods and applications

Abstract

This application provides a composite functional material loaded with gadolinium, bismuth, and boron, its preparation method, and applications, belonging to the field of functional fibers and polymer composite materials. Specifically, gadolinium and bismuth source powders are surface-modified and blended with a polymer matrix, then wet-spun to form gadolinium and bismuth-loaded functional fibers, which are then woven into fabrics. Boron source powder is surface-pretreated and dispersed in liquid rubber to obtain a high-abundance boron-containing composite material. 10 A functional adhesive containing boron compounds is then applied; the functional fiber fabric is immersed in this adhesive, followed by vacuum-assisted impregnation and curing to obtain a composite functional material loaded with gadolinium, bismuth, and boron. This composite functional material loaded with gadolinium, bismuth, and boron solves the problem of uneven dispersion in multi-filler blending through a functional partition structure design, and strengthens interfacial bonding through surface modification and vacuum impregnation processes, thereby achieving a balance between high uniformity of protective performance and mechanical flexibility. It is suitable for multiple fields such as medical protection, industrial testing, and aerospace.

Description

Technical Field

[0001] This invention relates to the field of functional fiber and polymer composite materials technology, specifically to a composite functional material loaded with gadolinium, bismuth and boron, its preparation method and application. Background Technology

[0002] With the development of polymer processing technology, composite fibers loaded with inorganic functional powders and their reinforced composite materials have been widely used in medical, aerospace, and industrial protection fields. Wet spinning technology, with its ability to achieve uniform dispersion of highly filled powders at low temperatures, has become the mainstream method for preparing high-performance functional fibers.

[0003] Existing high-filler inorganic functional composite materials face two major technological bottlenecks: First, the mutual interference and uneven dispersion of multi-component powders during blending lead to inconsistent distribution of functional powders, resulting in high spinning breakage rates, difficulties in continuous production, and localized fluctuations in the concentration of effective functional elements, resulting in unstable protective performance and low overall efficiency. Second, the weak interfacial bonding in the layered structure makes interlayer separation prone to occur, leading to deterioration of the material's mechanical properties, shortened service life, and the formation of weak zones at the interfaces, reducing overall protective reliability. These problems prevent existing materials from simultaneously achieving high uniformity of protective performance and excellent mechanical flexibility in a single flexible thin layer. Current technologies generally adopt a design approach of blending multiple fillers in a single matrix, failing to recognize the inherent conflict in the performance requirements of different functional fillers. Deploying fillers with different functions in different matrices is the fundamental way to simultaneously solve the problems of uneven dispersion and performance dilution among multiple fillers, making it difficult to meet the urgent needs of medical, industrial, and other fields for lightweight, highly reliable, and multifunctional composite materials. Summary of the Invention

[0004] In view of the technical problems existing in the background art, this application provides a composite functional material loaded with gadolinium, bismuth and boron, its preparation method and application. The composite functional material loaded with gadolinium, bismuth and boron solves the problem of uneven dispersion of multiple fillers through functional partition structure design, and strengthens the interface bonding through surface modification and vacuum impregnation process, thereby achieving a unity of high uniformity protective performance and mechanical flexibility. It is suitable for multiple fields such as medical protection, industrial testing, and aerospace.

[0005] To achieve the above objectives, in a first aspect, this application provides a method for preparing a composite functional material loaded with gadolinium, bismuth, and boron, comprising: It provides gadolinium source powder, bismuth source powder, first surface modifier solution, second surface modifier solution, boron source powder, polymer solution, liquid rubber, vulcanizing compounding agent and antioxidant; Gadolinium source powder and bismuth source powder were pretreated with a first surface modifier solution to obtain a composite modified powder of gadolinium source and bismuth source. A spinning solution is obtained by mixing a composite modified powder of gadolinium source and bismuth source with a polymer solution. Functional fiber fabrics are obtained by wet spinning of the spinning solution and then weaving. Boron source powder is pretreated with a second surface modifier solution to obtain modified boron source powder; Modified boron source powder is dispersed in liquid rubber, and vulcanizing compounding agent and antioxidant are added to obtain functional rubber liquid; Under vacuum, functional fiber fabrics are immersed in a functional adhesive solution, then removed and cured to obtain a composite functional material loaded with gadolinium, bismuth, and boron; among which, The molar ratio of bismuth in the bismuth source to gadolinium in the gadolinium source is (1-4):1; The mass ratio of the gadolinium source and bismuth source composite modified powder to the polymer is (60-75):(25-40); In functional adhesives, the mass percentage of modified boron source powder is 40%-60%. The mass ratio of functional fiber fabric to functional adhesive is (4-6):(4-6).

[0006] Furthermore, the gadolinium source powder includes at least one of gadolinium oxide, gadolinium nitrate, and gadolinium hydroxyoxide, and the bismuth source powder includes at least one of bismuth oxide, bismuth nitrate, bismuth tungstate, and bismuth powder.

[0007] Furthermore, the first surface modifier solution includes a first surface modifier and a first solvent. The first surface modifier includes at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. The mass of the first surface modifier is 1%-5% of the total mass of the gadolinium source powder and the bismuth source powder. In the first surface modifier solution, the mass percentage of the first surface modifier is 3%-8%.

[0008] Furthermore, the polymer solution includes a polymer and a second solvent, wherein the polymer includes at least one of polyacrylonitrile, polyvinyl alcohol, polyurethane, polyamide and cellulose, and the polymer mass percentage in the polymer solution is 18%-25%.

[0009] Furthermore, the coagulation bath in wet spinning includes at least one of water, ethanol, dimethylacetamide aqueous solution, and dimethyl sulfoxide aqueous solution; the draw ratio of the coagulation bath in wet spinning is 1.5-5; the temperature of the coagulation bath in wet spinning is 50℃-70℃; the fiber diameter obtained by wet spinning is 100μm-800μm; the thickness of the functional fiber fabric is 0.5mm-2mm; and the areal density of the functional fiber fabric is 100g / m³. 2 -1000g / m 2 .

[0010] Furthermore, the boron source includes at least one of boron carbide, boron nitride, boric acid, and boron oxide, and10 The abundance of B is ≥80%. The second surface modifier solution includes a second surface modifier and a third solvent. The second surface modifier includes at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent. The mass of the second surface modifier is 1%-5% of the mass of the boron source powder. In the second surface modifier solution, the mass percentage of the second surface modifier is 3%-8%.

[0011] Furthermore, the liquid rubber includes at least one of natural rubber latex, styrene-butadiene rubber latex, carboxylated nitrile rubber latex, chloroprene rubber latex, and liquid silicone rubber. The vulcanizing compounding agent includes sulfur, zinc oxide, and an accelerator. In the functional rubber liquid, the mass percentage of the antioxidant is 0.5%-1%, the mass percentage of sulfur is 0.5%-2%, the mass percentage of zinc oxide is 0.5%-2%, and the mass percentage of the accelerator is 0.1%-1%.

[0012] Furthermore, the gauge pressure under vacuum is (-0.06MPa) to (-0.095MPa), the impregnation time is 5 min to 30 min, the curing temperature is 80℃ to 160℃, and the curing time is 60 min to 90 min.

[0013] Secondly, this application also provides a composite functional material supported on gadolinium, bismuth, and boron, prepared by any of the methods described above for preparing composite functional materials supported on gadolinium, bismuth, and boron. The thickness of the composite functional material supported on gadolinium, bismuth, and boron is 0.8 mm to 3 mm, the tensile strength of the composite functional material supported on gadolinium, bismuth, and boron is ≥12 MPa, and the areal density of the composite functional material supported on gadolinium, bismuth, and boron is 1 kg / m³. 2 -3kg / m 2 .

[0014] Thirdly, this application also provides an application of a composite functional material loaded with gadolinium, bismuth and boron, which is used to prepare interventional protective gloves, thyroid protective neck warmers, protective clothing for medical staff in nuclear medicine departments, protective curtains for industrial non-destructive testing, flexible wrapping materials, aerospace protective equipment or emergency protective equipment.

[0015] The beneficial effects of this application are as follows: In this application's technical solution, gadolinium and bismuth are specifically enriched in the fiber fabric phase, while boron is specifically dispersed in the liquid rubber matrix phase. This allows the two functional components to be spatially partitioned and non-interfering, resolving the inherent contradiction of mutual interference among multiple fillers in traditional blending systems from a material structure design perspective. This solution employs a surface modification process using surface modifiers to improve the interfacial compatibility between the inorganic powder and the organic polymer matrix, achieving uniform dispersion of gadolinium and bismuth composite oxides in the fibers at a high filler content of 60%-75%. Through a liquid rubber vacuum-assisted impregnation process, the functional adhesive completely fills all pores within the functional fiber fabric. After curing, a three-dimensional interlocking structure is formed between the impregnated matrix and the fiber fabric, resulting in strong interfacial bonding and no interlayer separation issues, ensuring continuous and uniform distribution of the functional material throughout the entire spatial range of the composite material. The fibers exhibit stable mechanical properties, allowing for continuous weaving and providing long-term service stability for the gadolinium and bismuth functional powders. The composite functional material loaded with gadolinium, bismuth and boron is a thin-layer lightweight structure that combines high elasticity, bendability and lead-free, non-toxic and environmentally friendly advantages. While meeting multi-dimensional performance requirements, it also takes into account flexibility and wearing comfort. By controlling the molar ratio of bismuth in the bismuth source to gadolinium in the gadolinium source within the range of (1-4):1, it can provide medium and high energy photon attenuation with bismuth as the main component and enhance the low energy absorption efficiency with gadolinium as a supplement, forming a continuous broadband protection chain.

[0016] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.

[0018] Figure 1 This is a scanning electron microscope image of the surface-modified boron nitride powder of this application; Figure 2 This is a scanning electron microscope image of the surface-modified bismuth oxide powder of this application; Figure 3 This is a scanning electron microscope image of the surface-modified gadolinium oxide powder of this application; Figure 4 This is a photograph of the functional fiber fabric prepared by hand weaving in Example 1 of this application; Figure 5 This is a scanning electron microscope image of the functional fiber fabric of Embodiment 1 of this application; Figure 6 This is a scanning electron microscope image of the cross-section of the functional fiber fabric of Embodiment 1 of this application; Figure 7 This is a physical image of the composite functional material loaded with gadolinium, bismuth, and boron according to Embodiment 1 of this application; Figure 8 This is a scanning electron microscope image of the cross-section of the composite functional material loaded with gadolinium, bismuth and boron in Embodiment 1 of this application. Detailed Implementation

[0019] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0021] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0022] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0023] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship.

[0024] To address the technical problems of mutual interference, uneven dispersion, weak interfacial bonding in layered structures, and easy interlayer separation during multi-component powder blending, which reduces the overall protective reliability, this application provides, in a first aspect, a method for preparing a composite functional material loaded with gadolinium, bismuth, and boron, comprising: It provides gadolinium source powder, bismuth source powder, first surface modifier solution, second surface modifier solution, boron source powder, polymer solution, liquid rubber, vulcanizing compounding agent and antioxidant; Gadolinium source powder and bismuth source powder were pretreated with a first surface modifier solution to obtain a composite modified powder of gadolinium source and bismuth source. A spinning solution is obtained by mixing a composite modified powder of gadolinium source and bismuth source with a polymer solution. Functional fiber fabrics are obtained by wet spinning of the spinning solution and then weaving. Boron source powder is pretreated with a second surface modifier solution to obtain modified boron source powder; Modified boron source powder is dispersed in liquid rubber, and vulcanizing compounding agent and antioxidant are added to obtain functional rubber liquid; Under vacuum, functional fiber fabrics are immersed in a functional adhesive solution, then removed and cured to obtain a composite functional material loaded with gadolinium, bismuth, and boron; among which, The molar ratio of bismuth in the bismuth source to gadolinium in the gadolinium source is (1-4):1; The mass ratio of the gadolinium source and bismuth source composite modified powder to the polymer is (60-75):(25-40); In functional adhesives, the mass percentage of modified boron source powder is 40%-60%. The mass ratio of functional fiber fabric to functional adhesive is (4-6):(4-6).

[0025] In this application's technical solution, gadolinium and bismuth are specifically enriched in the fiber fabric phase, while boron is specifically dispersed in the liquid rubber matrix phase. This allows the two functional components to be spatially partitioned and non-interfering, resolving the inherent contradiction of mutual interference among multiple fillers in traditional blending systems from a material structure design perspective. This solution employs a surface modification process using surface modifiers to improve the interfacial compatibility between the inorganic powder and the organic polymer matrix, achieving uniform dispersion of gadolinium and bismuth composite oxides in the fibers at a high filler content of 60%-75%. Through a liquid rubber vacuum-assisted impregnation process, the functional adhesive completely fills all pores within the functional fiber fabric. After curing, a three-dimensional interlocking structure is formed between the impregnated matrix and the fiber fabric, resulting in strong interfacial bonding and no interlayer separation issues, ensuring continuous and uniform distribution of the functional material throughout the entire spatial range of the composite material. The fibers exhibit stable mechanical properties, allowing for continuous weaving and providing long-term service stability for the gadolinium and bismuth functional powders. The composite functional material loaded with gadolinium, bismuth and boron is a thin-layer lightweight structure that combines high elasticity, bendability and lead-free, non-toxic and environmentally friendly advantages. While meeting multi-dimensional performance requirements, it also takes into account flexibility and wearing comfort. By controlling the molar ratio of bismuth in the bismuth source to gadolinium in the gadolinium source within the range of (1-4):1, it can provide medium and high energy photon attenuation with bismuth as the main component and enhance the low energy absorption efficiency with gadolinium as a supplement, forming a continuous broadband protection chain.

[0026] It is understandable that the gadolinium source and bismuth source composite modified powder is a mixed powder after modification according to a certain molar ratio, which includes modified gadolinium source powder and modified bismuth source powder.

[0027] It can be explained that wet spinning involves extruding the spinning solution from the small holes of the spinneret into a liquid called a "coagulation bath," where it eventually coagulates into solid fibers.

[0028] It can be explained that the purpose of pretreating the gadolinium source powder and bismuth source powder with the first surface modifier solution is to reduce the high surface energy of the nanoparticles, reduce the tendency of powder aggregation, and enhance the interfacial compatibility between inorganic powder and organic polymer matrix, thus laying the foundation for the uniform and stable dispersion of powder in the spinning solution during the subsequent wet spinning process. The pretreatment operation includes, but is not limited to, placing bismuth source powder and gadolinium source powder in a high-speed mixer in a molar ratio, spraying a surface modifier solution while stirring, wherein the solvent of the surface modifier solution is ethanol, deionized water or ethanol-water mixture, the mass percentage of the surface modifier in the surface modifier solution is 3%-8%, and the amount of surface modifier is 1%-5% of the total mass of gadolinium source and bismuth source, stirring and mixing at 60℃-100℃ for 20min-60min, and then drying at 80℃-120℃ to constant weight to obtain surface-modified gadolinium-bismuth composite powder.

[0029] It can be explained that the boron source powder is pretreated with a second surface modifier solution. The pretreatment operation includes, but is not limited to, adding the boron source powder to ethanol or ethanol-water solution containing a surface modifier. The surface modifier in the surface modifier solution has a mass percentage of 3%-8% and the amount of surface modifier is 1%-5% of the mass of the boron source powder. The mixture is stirred and dispersed at room temperature to 60°C for 30-120 minutes, filtered, or dried directly at 80°C-120°C to constant weight to obtain modified boron source powder.

[0030] It is understood that the first surface modifier and the second surface modifier can be selected the same or different. The first surface modifier can be selected from at least one of silane coupling agents, titanate coupling agents and aluminate coupling agents, and the second surface modifier can be selected from at least one of silane coupling agents, titanate coupling agents and aluminate coupling agents; wherein, the silane coupling agent includes at least one of KH550, KH560, KH570 and A171.

[0031] It can be explained that, under vacuum, functional fiber fabric is immersed in functional adhesive solution, and after curing, a composite functional material loaded with gadolinium, bismuth and boron is obtained. After the impregnated fabric is taken out, the adhesive content and surface smoothness can be controlled by scraping or rolling, so that the functional adhesive solution fills the pores of the functional fiber fabric and controls the functional adhesive solution to form a coating layer on the fabric surface of the functional fiber fabric. The thickness of the coating layer is between 0.15mm and 0.5mm, and the mass ratio of functional fiber fabric to functional adhesive solution is (4-6): (4-6).

[0032] In some embodiments, the gadolinium source powder includes at least one of gadolinium oxide, gadolinium nitrate, and gadolinium hydroxyoxide, and the bismuth source powder includes at least one of bismuth oxide, bismuth nitrate, bismuth tungstate, and bismuth powder.

[0033] In this embodiment, the composite system of gadolinium oxide and bismuth oxide is selected based on their synergistic and complementary mechanism in broad-spectrum X-ray shielding. The K-layer absorption edge of gadolinium oxide is approximately 50.2 keV, exhibiting extremely high photoelectric absorption efficiency for low-energy X-rays; the K-layer absorption edge of bismuth oxide is approximately 90.5 keV, and its L-layer absorption edge is approximately 13-16 keV, forming a relay coverage with the absorption edge of gadolinium oxide, effectively filling the shielding efficiency gap in the 50-100 keV energy range, thereby improving the X-ray and gamma-ray shielding efficiency of the composite functional material loaded with gadolinium, bismuth, and boron.

[0034] In some embodiments, the first surface modifier solution includes a first surface modifier and a first solvent. The first surface modifier includes at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. The mass of the first surface modifier is 1%-5% of the total mass of the gadolinium source powder and the bismuth source powder. In the first surface modifier solution, the mass percentage of the first surface modifier is 3%-8%.

[0035] In this embodiment, a silane coupling agent is selected. After hydrolysis of the alkoxy groups in its molecule, it can form covalent bonds with the hydroxyl groups on the surface of the bismuth source powder and gadolinium source powder, resulting in a strong interfacial bond. A titanate coupling agent is selected, which reacts with free protons on the surface of inorganic materials to form a dense organic monolayer, thereby changing its surface properties, reducing the surface energy of the bismuth source powder and gadolinium source powder and the viscosity of the system. An aluminate coupling agent is selected, which can reduce the water absorption and oil absorption of the composite material and improve its physical and mechanical properties and gloss. The amount of the first surface modifier is controlled at 1%-5% of the total powder mass. The modification effect is appropriate. The first surface modifier will not condense with the excess surface modifier molecules to form oligomers, which improves the dispersibility of gadolinium source powder and bismuth source powder. This improves the dispersion uniformity of bismuth source powder and gadolinium source powder in the composite functional material loaded with gadolinium, bismuth and boron, enhances the stability of gadolinium source powder and bismuth source powder in the composite functional material, improves the X-ray shielding efficiency and γ-ray shielding efficiency of the composite functional material loaded with gadolinium, bismuth and boron, and can also improve the mechanical properties of the composite functional material loaded with gadolinium, bismuth and boron.

[0036] In some embodiments, the polymer solution includes a polymer and a second solvent, wherein the polymer includes at least one selected from polyacrylonitrile, polyvinyl alcohol, polyurethane, polyamide and cellulose, and the polymer in the polymer solution is 18%-25% by mass.

[0037] In this embodiment, a polymer is used as the matrix, which can provide film-forming properties, mechanical support and processing performance, adapt to different processing scenarios, enhance the stability of gadolinium source powder and bismuth source powder in composite functional materials, improve the X-ray shielding efficiency and γ-ray shielding efficiency of composite functional materials loaded with gadolinium, bismuth and boron, and improve the mechanical properties of composite functional materials loaded with gadolinium, bismuth and boron.

[0038] In some embodiments, the coagulation bath in wet spinning includes at least one of water, ethanol, an aqueous solution of dimethylacetamide, and an aqueous solution of dimethyl sulfoxide; the draw ratio of the coagulation bath in wet spinning is 1.5-5; the temperature of the coagulation bath in wet spinning is 50℃-70℃; the fiber diameter obtained by wet spinning is 100μm-800μm; the thickness of the functional fiber fabric is 0.5mm-2mm; and the areal density of the functional fiber fabric is 100g / m³. 2 -1000g / m 2 .

[0039] In this embodiment, the wet spinning process achieves uniform and stable dispersion of high-filling-weight functional powders in fibers through low-temperature double-diffusion solidification. The dimethylacetamide aqueous solution and the polyacrylonitrile spinning solution share the same solvent system, facilitating the control of the double-diffusion rate and resulting in fibers with a dense structure and rounded cross-section. The process window is wide and its industrial applicability is good. The draw ratio is controlled between 1.5 and 5.0 times; stretching causes the internal molecular chains of the fiber to align axially, improving the fiber's mechanical strength. As an aggregate of fibers and a flexible skeleton, the fabric's structure can influence the penetration efficiency of subsequent functional adhesives and the mechanical flexibility of the composite material. By controlling the fiber diameter, functional fiber fabric thickness, and areal density within a certain range, this parameter range can balance the stability of spinning production with the uniform dispersion of powder, enhance the interfacial bonding force between the fiber and the rubber matrix and the penetration performance of the adhesive, and improve the uniformity of protection. At the same time, it matches the vacuum impregnation process window to maintain the basic mechanical skeleton strength and basic protective capacity of the functional fiber fabric, and can maintain sufficient functional adhesive penetration. The thickness of the composite material can be adjusted to adapt to different application scenarios. Furthermore, it can achieve a balance between protective performance and lightweight, covering the needs of multiple scenarios with different protection levels. The synergistic effect of these three factors achieves the unity of spinnability, protective performance, mechanical properties, and wearing comfort.

[0040] In some embodiments, the second surface modifier solution includes a second surface modifier and a third solvent. The second surface modifier includes at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. The mass of the second surface modifier is 1%-5% of the mass of the boron source powder. In the second surface modifier solution, the mass percentage of the second surface modifier is 3%-8%.

[0041] In this embodiment, high abundance 10 B can enhance the thermal neutron absorption efficiency of composite materials. 10 Boron (B) has a higher thermal neutron absorption cross section than boron with natural abundance (approximately 19.9%), which can improve the neutron shielding performance of composite materials at the same boron content, reducing filler usage and material thickness. Boron carbide has high hardness and chemical stability, boron nitride has good thermal conductivity and insulation, and boric acid and boron oxide have easy processability. These can be flexibly selected according to different polymer matrices and molding processes to improve the thermal neutron absorption efficiency of composite materials. Modifying boron source powder can improve the dispersion uniformity of boron source powder in liquid rubber, reduce boron source powder agglomeration, and improve the mechanical properties of composite functional materials loaded with gadolinium, bismuth, and boron.

[0042] In some embodiments, the liquid rubber includes at least one of natural latex, styrene-butadiene latex, carboxylated nitrile latex, chloroprene latex, and liquid silicone rubber, and the vulcanizing compounding agent includes sulfur, zinc oxide, and an accelerator. In the functional rubber liquid, the mass percentage of antioxidant is 0.5%-1%, the mass percentage of sulfur is 0.5%-2%, the mass percentage of zinc oxide is 0.5%-2%, and the mass percentage of accelerator is 0.1%-1%.

[0043] In this embodiment, the liquid rubber possesses film-forming properties, room temperature curing ability, and flexibility, enabling it to encapsulate highly filled modified boron functional powders and form a continuous elastic shielding layer. Natural latex and styrene-butadiene latex are low-cost and easy to process; carboxylated nitrile butadiene latex contains polar functional groups, exhibiting stronger powder bonding and oil resistance; chloroprene latex provides flame retardancy to the composite material; and liquid silicone rubber possesses high and low temperature resistance and chemical stability. Sulfur, as a vulcanizing agent, enables the formation of cross-links between rubber molecular chains, providing the material with elasticity and mechanical strength. Zinc oxide, as a activator, reacts with stearic acid to generate zinc soap, improving cross-linking efficiency and the uniformity of cross-linking density. Antioxidants can delay the oxidative aging of rubber during processing and use; selectable antioxidants include at least one of N-isopropyl-N'-phenyl-p-phenylenediamine, dilauryl thiodipropionate, zinc diethyldithiocarbamate, and distearate thiodipropionate. Within the specified range, the dosage of each compounding agent can ensure sufficient vulcanization of the impregnating solution and complete crosslinking network. Selectable accelerators include at least one of n-butyraldehyde aniline condensate, sodium di-n-butyl dithiocarbamate, and 2,2,4-trimethyl-1,2-dihydroquinoline polymer.

[0044] In some embodiments, the gauge pressure under vacuum is (-0.06MPa) to (-0.095MPa), the impregnation time is 5 min to 30 min, the curing temperature is 80℃ to 160℃, and the curing time is 60 min to 90 min.

[0045] In this embodiment, a vacuum-assisted impregnation process is employed. The pressure difference between the inside and outside of the fabric drives the functional adhesive to penetrate all the pores of the fabric, including the tiny gaps within the fiber bundles, resulting in a continuous and uniform distribution of the thermal neutron-absorbing material throughout the composite material space. Appropriate vacuum levels and impregnation time allow the adhesive to fully fill the tiny voids deep within the fabric. After impregnation, excess adhesive is removed by scraping or rolling to smooth the surface, forming a continuous polymer coating layer of approximately 0.15mm-0.5mm on both sides of the fabric.

[0046] Secondly, this application also provides a composite functional material supported on gadolinium, bismuth, and boron, prepared by any of the methods described above for preparing composite functional materials supported on gadolinium, bismuth, and boron. The thickness of the composite functional material supported on gadolinium, bismuth, and boron is 0.8 mm to 3 mm, the tensile strength of the composite functional material supported on gadolinium, bismuth, and boron is ≥12 MPa, and the areal density of the composite functional material supported on gadolinium, bismuth, and boron is 1 kg / m³. 2 -3kg / m 2 .

[0047] In the technical solution of this application embodiment, gadolinium and bismuth-containing wet-spun fibers are woven into a fabric as an X-ray and gamma-ray shielding skeleton. Boron-containing liquid rubber is vacuum-assisted impregnated to fill the pores of the fabric and coat the surface as a thermal neutron absorbing matrix. The resulting composite material achieves the partitioned deployment and synergistic integration of broad-spectrum X-ray attenuation and thermal neutron capture in the same flexible thin-layer material. When X-rays and gamma rays penetrate the composite material, they are first efficiently attenuated by the gadolinium and bismuth-containing nanoparticles uniformly embedded in the fiber fabric through photoelectric effect and Compton scattering. Among them, gadolinium oxide and bismuth oxide form a broad-spectrum continuous shielding chain using their respective K-layer absorption edges (approximately 50.2 keV and 90.5 keV, respectively). When thermal neutrons pass through, they are absorbed by the boron-impregnated matrix. 10 B(n,α) 7 Li nucleus reaction capture, the reaction products are charged heavy particles (alpha particles and...) 7 The Li nucleus does not produce highly penetrating secondary gamma rays. The two protective functional components are spatially independent and each performs its own function, overcoming the inherent defects of traditional blending systems where functional fillers dilute each other and their effects are mutually exclusive. This achieves synergistic radiation protection across the entire spectrum while maintaining the overall lightweight and flexibility of the material. This functional zoning design can improve X-ray shielding efficiency by more than 20% at the same areal density, while maintaining thermal neutron shielding efficiency above 99% and increasing tensile strength by at least 50%.

[0048] It can be explained that the photoelectric effect refers to the phenomenon that when light (electromagnetic radiation) shines on the surface of a metal material, a photon transfers all its energy to an electron, and the electron, after gaining energy, escapes from the atom and becomes a free electron.

[0049] It can be explained that Compton scattering efficient attenuation refers to the rapid transfer of energy to electrons through the Compton scattering process when high-energy photons (such as X-rays and gamma rays) interact with matter, thereby reducing the energy and intensity of the incident photons.

[0050] Thirdly, this application also provides an application of a composite functional material loaded with gadolinium, bismuth and boron, which is used to prepare interventional protective gloves, thyroid protective neck warmers, protective clothing for medical staff in nuclear medicine departments, protective curtains for industrial non-destructive testing, flexible wrapping materials, aerospace protective equipment or emergency protective equipment.

[0051] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0052] I. Testing Methods 1. Radiation Shielding Performance Test: The sample was cut into pieces with dimensions of 10cm x 10cm and a thickness of 2mm. Following the narrow-beam transmission method in "YY / T0292.1-2020 Medical Diagnostic X-ray Radiation Protection Apparatus: Part 1: Determination of Material Attenuation Performance", the incident and transmitted dose rates of 65keV X-rays, 120keV X-rays, and 662keV 137Cs-γ-rays were tested respectively. The shielding efficiency was calculated using the following formula: Where I0 is the incident dose rate without a sample, and I is the transmitted dose rate with a sample.

[0053] 2. Thermal Neutron Shielding Performance Test: Following the gold foil activation method in ASTM E262-17, "Standard Method for Measuring Thermal Neutron Reactivity by Radioactive Counting Technique," the incident and transmitted activation count rates of 0.025 eV thermal neutrons were tested, and the thermal neutron shielding efficiency was calculated. The formula for calculating thermal neutron shielding efficiency is as follows: Where A0 is the activation count rate of the gold foil without a sample, and A is the activation count rate of the gold foil with a sample.

[0054] 3. Tensile property test: According to GB / T528-2009 Vulcanized rubber or thermoplastic rubber: Determination of tensile stress-strain properties, the specimen is cut into a standard shape of type 1, and the tensile strength is tested using a universal electronic tensile testing machine at a tensile speed of 500 mm / min. The effective number of repeated tests is ≥5 times, and the arithmetic mean of all effective data is taken as the final result.

[0055] The tensile strength of the fiber was tested according to the method published in GB / T 14344-2022 Chemical Fibers: Test Method for Tensile Properties of Filaments. The test was repeated ≥5 times, and the arithmetic mean of all valid data was taken as the final result.

[0056] II. Preparation Method Example 1 Preparation of polyacrylonitrile fibers from gadolinium oxide and bismuth oxide by wet spinning: 23.30 g (0.05 mol, purity ≥99.9%) of bismuth oxide and 18.13 g (0.05 mol, purity ≥99.9%) of gadolinium oxide were placed in a high-speed mixer. While stirring, 25 g of a 5% (w / v) silane coupling agent KH570 ethanol-water solution (volume ratio 1:1), pre-adjusted to pH 4.5 with glacial acetic acid, was sprayed in. The mixture was stirred at 80 °C for 40 min and then dried at 100 °C to constant weight, yielding 40.27 g of gadolinium and bismuth source composite modified powder. The gadolinium and bismuth source composite modified powder was added to 23.72 g of dimethylacetamide and ultrasonically dispersed for 60 min to form a uniform suspension. Simultaneously, 13.43 g of gadolinium oxide was added to dimethylacetamide. G of polyacrylonitrile powder (average molecular weight 149,000-151,000) was dissolved in 30g of pure dimethylacetamide. The powder suspension was slowly added to the polyacrylonitrile solution under continuous stirring for 4 hours. The solution was then degassed under vacuum at room temperature for 6 hours to obtain a spinning solution. The resulting spinning solution was spun into fibers using a wet spinning apparatus, with the metering pump output controlled at 3.0 mL / min. After filtration through a 20μm filter, the fibers were extruded through a 48-hole (0.8 mm) spinneret and formed in a 60℃ dimethylacetamide / water (volume ratio 65:35) coagulation bath. The nascent fibers were stretched 2.5 times, thoroughly washed with deionized water to remove residual solvent, and then dried at 80℃ to obtain continuous polyacrylonitrile fibers containing gadolinium oxide and bismuth oxide. The monofilament fineness was 12.5 dtex, the tensile strength was 2.8 cN / dtex, the elongation at break was 17.6%, and the fiber exhibited good flexibility, meeting the requirements for both hand weaving and industrial weaving.

[0057] Weaving of functional fiber fabrics: Polyacrylonitrile continuous fibers containing gadolinium oxide and bismuth oxide were used to prepare fabric samples by hand plain weaving. The fabric size was about 10cm×10cm, the thickness was about 0.5mm, and the areal density was about 420g / m². There was no fiber breakage during the weaving process, and the fabric structure was uniform.

[0058] Preparation of functional adhesive: Add 50g of boron nitride powder ( 10Boron nitride (B abundance ≥ 80%) was added to 50g of an ethanol-water solution (volume ratio 9:1, pH pre-adjusted to 4.5 with glacial acetic acid) containing 5wt% KH550 silane coupling agent. The mixture was stirred at room temperature for 60min and dried at 80℃ to constant weight to obtain modified boron nitride powder. 52.25g of natural latex (solid content 60%) was taken, and the modified boron nitride powder, 0.66g of sulfur, 0.66g of zinc oxide, 0.33g of zinc diethyldithiocarbamate, and 0.33g of 2,2,4-trimethyl-1,2-dihydroquinoline polymer were added sequentially under stirring. The mixture was stirred and dispersed for 30min, and then degassed under vacuum to obtain a uniform boron nitride-containing functional adhesive solution.

[0059] Impregnation and curing: 4.2g of boron nitride functional adhesive was poured into a 12cm×12cm stainless steel impregnation tray. 4.2g of functional fiber fabric was laid flat in the adhesive and pre-impregnated at normal pressure for 2 minutes. Then, the tray was placed in a vacuum dryer and vacuumed to -0.08MPa and maintained for 10 minutes to remove air from the fabric pores and allow the adhesive to fully penetrate. After the vacuum was removed, the fabric was left to stand for 3 minutes. The fabric pieces were then removed one by one and squeezed by double rollers with a roller gap of 0.8mm to remove excess adhesive. Finally, the fabric was laid flat on a polytetrafluoroethylene plate and placed in a forced-air drying oven to be heated and cured at 120℃ for 60 minutes. After naturally cooling to room temperature, the composite functional material loaded with gadolinium, bismuth and boron in Example 1 was obtained.

[0060] Appendix Figure 1 This is a scanning electron microscope (SEM) image of the boron nitride powder after surface modification with silane coupling agent KH550 in Example 1. The image shows a typical two-dimensional lamellar structure with uniform lamellar diameter distribution, smooth and flat surface, and clear edges of the lamellar particles. No particle adhesion due to surface modification is observed, indicating that the modification process reduced the surface energy of the boron nitride powder.

[0061] Appendix Figure 2 This is a scanning electron microscope (SEM) image of bismuth oxide powder after surface modification with silane coupling agent KH570 in Example 1. The bismuth oxide powder exhibits an irregular, near-spherical / blocky particle morphology, without a distinct layered structure, and is coated with a uniform coupling agent modification layer. No particle adhesion due to excessive modifier is observed. The particles show good dispersibility, with clear boundaries between individual particles and no large-area agglomerates.

[0062] Appendix Figure 3This is a scanning electron microscope (SEM) image of gadolinium oxide powder after surface modification with silane coupling agent KH570 in Example 1. The gadolinium oxide powder exhibits a typical layered stacked structure, consisting of irregular sheet-like / block-like particles. Most particles have clear parallel layering textures, with small fragments at the edges resulting from layered exfoliation. No obvious hard agglomeration is observed; all particles exist as independent individuals with clear boundaries and no large-area adhesion or clumping. The particle surface is rough, with abundant layered steps and folds, and no obvious smooth cleavage surfaces, indicating that the surface modifier has been uniformly coated on the particle surface.

[0063] Appendix Figure 4 The image shows a physical picture of the functional fiber fabric prepared by hand weaving in Example 1. The fabric in the picture has a plain weave structure, is uniformly light white, has a smooth and clean surface, and has no obvious weaving defects; the warp and weft yarns are clearly interwoven, the structure is dense and has good flexibility, and can be freely bent and cut.

[0064] Appendix Figure 5 The image shown is a scanning electron microscope image of the functional fiber fabric prepared in Example 1. It shows the surface morphology of the fabric at low magnification. The diameter of the single fiber is uniform, about 500 μm. The fiber surface is smooth, with no powder precipitation or exposure, indicating that the wet spinning process has achieved stable embedding of gadolinium-bismuth composite oxide inside the fiber.

[0065] Appendix Figure 6 The image shows a scanning electron microscope (SEM) image of the cross-section of the functional fiber fabric prepared in Example 1. The image clearly shows that the fibers have a circular or near-circular cross-section and a dense structure. A large number of nano-sized gadolinium-bismuth composite oxide particles are uniformly dispersed within the fibers, with no obvious large-sized agglomerates or powder segregation along the fiber cross-section. This indicates the uniform dispersion of the functional powder in the polyacrylonitrile matrix under high filling weight.

[0066] Figure 7 This is a macroscopic image of the composite functional material loaded with gadolinium, bismuth, and boron prepared in Example 1. The material appears as a white, flexible sheet with a smooth and flat surface, free from molding defects such as bubbles, missing adhesive, and exposed fibers. The material can be bent and rolled arbitrarily without creases or delamination after bending, demonstrating its excellent flexibility, processability, and interfacial bonding strength.

[0067] Figure 8This is a scanning electron microscope (SEM) image of the cross-section of the composite functional material loaded with gadolinium, bismuth, and boron prepared in Example 1. The bright white area represents the polyacrylonitrile functional fiber yarn loaded with gadolinium-bismuth composite oxide, and the dark gray area represents the boron nitride-containing rubber matrix. The localized micro-gaps between the fiber yarn and the rubber matrix in the image are artifacts caused by the release of interfacial stress during sample preparation via liquid nitrogen cryogenic fracture, and are not intrinsic defects of the material. The rubber matrix has fully impregnated the fiber bundles and achieved complete coverage, without any unimpregnated dry spots or macroscopic pores. The boron nitride powder in the matrix is ​​uniformly dispersed without significant agglomeration. This image demonstrates the effectiveness of the vacuum-assisted impregnation process of this application, achieving a functional zoning design where the fibers are enriched with high atomic number oxides and the matrix disperses light element borides.

[0068] Comparative Example 1 Compared with Example 1, the only difference is that the bismuth oxide and gadolinium oxide powders are not surface modified, and the boron nitride is not surface modified. Otherwise, they are roughly the same as in Example 1, and will not be repeated here.

[0069] Comparative Example 2 Compared with Example 1, the only difference is that the modified composite powder and the modified boron nitride powder are added together to the natural rubber latex and stirred and dispersed. After adding the same vulcanizing compounding agent as in Example 1, a pure natural rubber latex film (excluding fiber fabric) is made by impregnation molding method with a film thickness of 2 mm. Other aspects are roughly the same as in Example 1, and will not be repeated here.

[0070] Comparative Example 3 Compared with Example 1, the only difference is that the modified composite powder and the modified boron nitride powder are added together to the polyacrylonitrile solution and mixed, and then wet-spun to directly produce fiber fabric without the subsequent impregnation step. The thickness of the fabric is 2 mm. Other aspects are roughly the same as in Example 1, and will not be repeated here.

[0071] Comparative Example 4 Compared with Example 1, the only difference is that the functional fiber fabric was tested for radiation shielding performance directly without impregnation treatment, and the fabric thickness was about 0.5 mm.

[0072] Comparative Example 5 Compared with Example 1, the only difference is that the functional adhesive is cast into a film separately without impregnating the fabric, and the film thickness is about 2 mm. Otherwise, it is roughly the same as Example 1, and will not be repeated here.

[0073] Comparative Example 6 Compared with Example 1, the only difference is that the functional fiber fabric is used as the middle layer, and the functional adhesive liquid is separately cast into films (each film thickness is about 0.8 mm) as the upper and lower layers. The three layers are uniformly coated and bonded with natural latex-based adhesive. Under a pressure of 0.5 MPa and hot-pressed at 80°C for 30 min, a layered laminated composite material with a total thickness of about 2 mm is obtained.

[0074] Table 1 shows the test data for Example 1 and Comparative Examples 1-6. As can be seen from the data in Table 1, the performance comparison of each embodiment and comparative example verifies the comprehensive advantages of the functional partition synergistic protection design of this scheme. Comparative Example 1 omits the surface modification of gadolinium source powder and bismuth source. The unmodified powder has poor compatibility with the matrix and serious agglomeration, resulting in simultaneous deterioration of shielding efficiency and tensile strength, indicating that surface modification is the key to improving powder dispersibility and interfacial compatibility. Comparative Examples 2 and 3 completely blend gadolinium oxide and bismuth oxide with boron nitride, abandoning the functional partition structure. All shielding efficiencies are lower than those of Example 1, indicating that there is an inherent contradiction between boron nitride and X-ray and γ-ray shielding fillers in the traditional blending system, and the mechanical properties decrease due to excessive agglomeration of fillers. Comparative Examples 4 and 5 omit the impregnation matrix and fiber fabric, respectively, indicating that the lack of any functional layer makes it impossible to achieve synergistic and efficient protection against X-rays, γ-rays and thermal neutrons. Comparative Example 6 uses layered bonding instead of integrated impregnation molding. The interlayer is only physically bonded, and the tensile strength is lower than that of Example 1, verifying the advantage of the in-situ impregnation-curing three-dimensional interlocking structure in terms of interfacial bonding strength.

[0075] Examples 2-7 and Comparative Examples 7 and 8 The only difference between Examples 2-7 and Comparative Examples 7 and 8 and Example 1 is that the molar ratio of bismuth in the bismuth source and gadolinium in the gadolinium source in the composite modified powder is different. Otherwise, they are roughly the same as Example 1 and will not be repeated here.

[0076] Table 2 shows the test data for Examples 1-7 and Comparative Examples 7 and 8. As shown in Table 2, under the premise of keeping other conditions unchanged, only changing the molar ratio of bismuth in the bismuth source to gadolinium in the gadolinium source, the properties of the composite material show a regular trend. The X-ray shielding efficiency of 65 keV increases continuously with the increase of gadolinium ratio. The K-layer absorption edge of gadolinium (about 50.2 keV) is located in the photoelectric effect advantage region of this energy, and has an extremely high photoelectric absorption cross section for low-energy X-rays. The X-ray shielding efficiency of 120 keV and the γ-ray shielding efficiency of 662 keV increase with the increase of bismuth ratio. The attenuation mechanism in this energy range is dominated by Compton scattering. The atomic number of bismuth (83) is higher than that of gadolinium (64), and the Compton scattering cross section per unit mass is larger. The higher the bismuth content, the stronger the attenuation ability for medium and high-energy photons. The thermal neutron shielding efficiency is achieved by the boron nitride functionalized adhesive impregnating the matrix, and its performance is unaffected by changes in the bismuth to gadolinium ratio in the fiber fabric layer. The neutron capture efficiency remains stable under different bismuth:gadolinium ratios, verifying that the functional partitioning design can achieve independent dispersion of the two functional powders without interference. Furthermore, the total filling amount of functional powders is consistent across all samples, resulting in stable and reliable mechanical properties of the composite material, with minimal overall variation in tensile strength.

[0077] Examples 8 and 9 and Comparative Examples 9-12 The only difference between Examples 8 and 9 and Comparative Examples 9-12 and Example 1 is that the mass ratio of the gadolinium source and bismuth source composite modified powder to the polymer is different. Otherwise, they are roughly the same as Example 1 and will not be repeated here.

[0078] Table 3 shows the test data for Examples 1, 8, and 9 and Comparative Examples 9-12. As shown in Table 3, the X-ray shielding efficiencies at 65keV, 120keV, and 662keV, as well as the gamma-ray shielding efficiencies, all increased with the increase of the filling amount of the composite modified powder containing gadolinium and bismuth sources, indicating an increase in the concentration of gadolinium oxide and bismuth oxide shielding elements. The thermal neutron shielding efficiency remained stable above 99.5% at all filling amounts, with minimal variation, indicating that changes in the filling amount of gadolinium oxide and bismuth oxide in the fiber had no effect on its performance. The tensile strength exhibited a peak variation pattern of first increasing and then decreasing. When the filling amount increased from 40% to 60%, the tensile strength gradually increased from 12.46 MPa to 17.28 MPa. At this point, the nanoparticles were uniformly dispersed in the polyacrylonitrile fiber matrix, playing a nano-reinforcing role. When the filling amount exceeded 60%, the strength began to decrease, and at 90%, it plummeted to 8.64 MPa. The fundamental reason is that the excessively high filling amount exceeded the dispersion limit of the surface modification. Under excessively high filling amounts, local agglomeration of the powder intensified, and the continuity of the matrix was damaged, becoming stress concentration points.

[0079] Examples 10 and 11 and Comparative Examples 13-16 Examples 10 and 11 and Comparative Examples 13-16 differ from Example 1 only in the mass percentage of the modified boron nitride powder in the functional adhesive, i.e., the filling amount. Otherwise, they are largely the same as Example 1 and will not be repeated here.

[0080] Table 4 shows the test data for Examples 1, 10, and 11, and Comparative Examples 13-16. As shown in the table above, the X-ray shielding efficiencies at 65keV and 120keV, and the gamma-ray shielding efficiencies at 662keV, show little change with increasing boron nitride content, further confirming the independence of the functional partition design and the fact that the functions of the fiber phase and the matrix phase do not interfere with each other. This scheme adopts a functional partition synergistic protection design. The X-ray and gamma-ray shielding functions are mainly undertaken by gadolinium oxide and bismuth oxide enriched in the functional fiber fabric layer. Changes in the boron nitride content in the impregnated matrix have limited impact on photon shielding capabilities. The thermal neutron shielding efficiency increases with increasing boron nitride content, rising from 76.58% at 20% to 88.71% at 40%, after which the rate of increase slows, reaching 99.58% at 60%, and approaching saturation at 80%. This is because the thermal neutron shielding performance improves with increasing boron nitride content. 10 Boron nitride (B) efficiently captures thermal neutrons through (n, α) nuclear reactions. Higher boron nitride content results in a greater density of thermal neutron absorption centers and a higher macroscopic reaction cross-section. However, tensile strength decreases with increasing boron nitride content, dropping from 19.31 MPa at 20% to 9.63 MPa at 80%. This is because while boron nitride's graphite-like layered structure provides flexibility and strength at low filler levels, its inorganic rigidity gradually disrupts the continuity and flexibility of the rubber molecular chains, increasing the matrix's stiffness and brittleness. This makes the composite more prone to stress concentration and interfacial debonding during tensile testing, leading to a decrease in tensile strength. In summary, a boron nitride filler content of 40%-60% achieves a balance between thermal neutron shielding performance and mechanical properties. Specifically, a 60% filler content achieves 99.58% efficient thermal neutron shielding while maintaining a tensile strength of 16.31 MPa.

[0081] Examples 12 and 13 and Comparative Examples 17-20 Examples 12 and 13 and Comparative Examples 17-20 differ from Example 1 only in the mass ratio of functional fiber fabric to functional adhesive; otherwise, they are largely the same as Example 1 and will not be repeated here.

[0082] Table 5 shows the test data for Examples 1, 12, and 13, and Comparative Examples 17-20. As shown in Table 5, the shielding efficiency for 65keV, 120keV X-rays, and 662keV gamma rays all decreases with increasing impregnation adhesive content. The attenuation function of X-rays and gamma rays is mainly provided by gadolinium oxide and bismuth oxide loaded in the fiber fabric layer. Increasing the proportion of functional adhesive leads to a higher relative content of the rubber matrix, a corresponding decrease in the volume fraction of the fiber layer in the composite material, and a reduction in the concentration of effective shielding elements participating in photon attenuation per unit thickness, resulting in a gradual decrease in the shielding efficiency of X-rays and gamma rays at each energy level.

[0083] The thermal neutron shielding efficiency increases monotonically with increasing functional adhesive content. The thermal neutron shielding capability depends on the amount of boron nitride in the system. 10 B-side density: The higher the content of functional adhesive, the thicker the boron-containing rubber matrix per unit area. 10 The density of the B-side increases accordingly, the density of thermal neutron absorption active sites increases, the macroscopic reaction cross section expands accordingly, and the thermal neutron shielding efficiency continues to rise.

[0084] The tensile strength exhibits a peak characteristic of first increasing and then decreasing with increasing functional adhesive content. When the adhesive content is low, the pores of the fiber fabric are not fully wetted and filled by the adhesive, and the remaining voids and dry spots hinder effective stress transfer between the fiber and the matrix, limiting the overall strength of the composite material. As the functional adhesive content gradually increases, the boron-containing rubber matrix completely penetrates and fills all the pores of the fabric, while forming a continuous coating layer on the fabric surface. A tight three-dimensional interlocking structure is constructed between the fiber and the rubber, significantly enhancing the interfacial bonding force, significantly improving stress transfer efficiency, and thus increasing the tensile strength. When the adhesive content exceeds 50%, the strength decreases. This is because the excessive proportion of rubber matrix weakens the skeletal load-bearing capacity of the fiber fabric, and the absolute amount of boron nitride increases synchronously with the adhesive content. Too many rigid particles exacerbate the brittleness of the matrix, leading to a decrease in overall strength.

[0085] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A method for preparing a composite functional material loaded with gadolinium, bismuth, and boron, characterized in that, include: It provides gadolinium source powder, bismuth source powder, first surface modifier solution, second surface modifier solution, boron source powder, polymer solution, liquid rubber, vulcanizing compounding agent and antioxidant; The gadolinium source powder and the bismuth source powder are pretreated with the first surface modifier solution to obtain a gadolinium source and bismuth source composite modified powder; The gadolinium source and bismuth source composite modified powder is mixed with the polymer solution to obtain a spinning solution; The spinning solution is wet-spun and then woven to obtain a functional fiber fabric. The boron source powder is pretreated with the second surface modifier solution to obtain modified boron source powder; The modified boron source powder is dispersed in the liquid rubber, and the vulcanizing compounding agent and the antioxidant are added to obtain a functional adhesive liquid; Under vacuum, the functional fiber fabric is immersed in the functional adhesive solution, then removed and cured to obtain a composite functional material loaded with gadolinium, bismuth, and boron; wherein, The molar ratio of bismuth in the bismuth source to gadolinium in the gadolinium source is (1-4):1; The mass ratio of the gadolinium source and bismuth source composite modified powder to the polymer is (60-75):(25-40). In the functional adhesive, the modified boron source powder accounts for 40%-60% by mass. The mass ratio of the functional fiber fabric to the functional adhesive is (4-6):(4-6).

2. The method for preparing the composite functional material loaded with gadolinium, bismuth, and boron according to claim 1, characterized in that, The gadolinium source powder includes at least one of gadolinium oxide, gadolinium nitrate, and gadolinium hydroxyoxide, and the bismuth source powder includes at least one of bismuth oxide, bismuth nitrate, bismuth tungstate, and bismuth powder.

3. The method for preparing the composite functional material loaded with gadolinium, bismuth, and boron according to claim 1, characterized in that, The first surface modifier solution includes a first surface modifier and a first solvent. The first surface modifier includes at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. The mass of the first surface modifier is 1%-5% of the total mass of the gadolinium source powder and the bismuth source powder. In the first surface modifier solution, the mass percentage of the first surface modifier is 3%-8%.

4. The method for preparing the composite functional material loaded with gadolinium, bismuth, and boron according to claim 1, characterized in that, The polymer solution comprises a polymer and a second solvent, wherein the polymer comprises at least one selected from polyacrylonitrile, polyvinyl alcohol, polyurethane, polyamide, and cellulose, and the polymer in the polymer solution is 18%-25% by mass.

5. The method for preparing the composite functional material supported on gadolinium, bismuth, and boron according to claim 1, characterized in that, The coagulation bath in the wet spinning process includes at least one of water, ethanol, dimethylacetamide aqueous solution, and dimethyl sulfoxide aqueous solution. The draw ratio of the coagulation bath in the wet spinning process is 1.5-5, the temperature of the coagulation bath in the wet spinning process is 50℃-70℃, the fiber diameter obtained by the wet spinning process is 100μm-800μm, the thickness of the functional fiber fabric is 0.5mm-2mm, and the areal density of the functional fiber fabric is 100g / m³. 2 -1000g / m 2 .

6. The method for preparing the composite functional material supported on gadolinium, bismuth, and boron according to claim 1, characterized in that, The boron source includes at least one of boron carbide, boron nitride, boric acid, and boron oxide, and 10 The abundance of B is ≥80%, the second surface modifier solution includes a second surface modifier and a third solvent, the second surface modifier includes at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent, the mass of the second surface modifier is 1%-5% of the mass of the boron source powder, and the mass percentage of the second surface modifier in the second surface modifier solution is 3%-8%.

7. The method for preparing the composite functional material supported on gadolinium, bismuth, and boron according to claim 1, characterized in that, The liquid rubber includes at least one of natural latex, styrene-butadiene latex, carboxylated nitrile latex, chloroprene latex, and liquid silicone rubber. The vulcanizing compounding agent includes sulfur, zinc oxide, and an accelerator. In the functional rubber solution, the antioxidant has a mass percentage of 0.5%-1%, the sulfur has a mass percentage of 0.5%-2%, the zinc oxide has a mass percentage of 0.5%-2%, and the accelerator has a mass percentage of 0.1%-1%.

8. The method for preparing the composite functional material supported on gadolinium, bismuth, and boron according to claim 1, characterized in that, The gauge pressure under vacuum is (-0.06MPa) to (-0.095MPa), the impregnation time is 5 min to 30 min, the curing temperature is 80℃ to 160℃, and the curing time is 60 min to 90 min.

9. A composite functional material loaded with gadolinium, bismuth, and boron, characterized in that, The composite functional material supported on gadolinium, bismuth, and boron is prepared by the method described in any one of claims 1-8, wherein the thickness of the composite functional material supported on gadolinium, bismuth, and boron is 0.8 mm-3 mm, the tensile strength of the composite functional material supported on gadolinium, bismuth, and boron is ≥12 MPa, and the areal density of the composite functional material supported on gadolinium, bismuth, and boron is 1 kg / m³. 2 -3kg / m 2 .

10. The application of the composite functional material supported on gadolinium, bismuth, and boron as described in claim 9, characterized in that, The composite functional material loaded with gadolinium, bismuth and boron is used to prepare interventional protective gloves, thyroid protective neck warmers, protective clothing for medical staff in nuclear medicine departments, protective curtains for industrial non-destructive testing, flexible wrapping materials, aerospace protective equipment or emergency protective equipment.

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