Protective composition, protective material and protective product

Abstract

The invention relates to the technical field of nuclear radiation protection, and provides a protective composition, a protective material and a protective product, the protective composition comprises the following components by weight: 80-120 parts of modified polyethylene fiber, 100-150 parts of a modified boron-containing compound, and 100-150 parts of a shield; the protective material comprises a base material and the protective composition, the protective product comprises the protective composition. The material prepared from the protection composition is ultra-light and ultra-soft, has good protection performance and better durability and functionality, and can be widely applied to neutron radiation protection products.

Description

Technical Field

[0001] This invention relates to the field of nuclear radiation protection technology, and more specifically, to a protective composition, protective material, and protective article. Background Technology

[0002] With the rapid development of the nuclear industry and nuclear technology applications, the field of radiation shielding and protection has attracted attention from all parties, resulting in huge financial investment and scientific research efforts, and has achieved a series of remarkable results.

[0003] In recent years, the protection of workers in environments involving thermal neutron radiation, such as nuclear energy utilization, nuclear medicine, and nuclear industrial facilities, has become crucial. Traditional neutron protective suits are often heavy, which not only affects workers' mobility but also increases physical exertion and reduces work efficiency over time. Furthermore, traditional protective suits lack flexibility; they do not adapt well to normal movements such as bending, raising arms, and turning, further limiting workers' freedom of movement. At the same time, most traditional protective suits offer insufficient neutron protection, with a protection efficiency below 92%, failing to meet increasingly stringent protection requirements. Therefore, developing an ultra-lightweight, ultra-soft thermal neutron protective suit with excellent protective performance has become an urgent technical challenge in this field. Summary of the Invention

[0004] The purpose of this invention is to provide a protective composition, protective material, and protective article. The material made from the protective composition is ultra-light and ultra-soft with good protective performance, better durability and functionality, and can be widely used in neutron radiation protection products.

[0005] The embodiments of the present invention are achieved through the following technical solutions:

[0006] A protective composition, by weight, comprises the following components: 80-120 parts of modified polyethylene fiber, 100-150 parts of modified boron-containing compound, and 100-150 parts of shielding material.

[0007] The modified polyethylene fiber is a polyethylene fiber with polydopamine surface modification, and the modified boron-containing compound is a boron-containing compound modified with hydroxyl-terminated polybutadiene.

[0008] Polyethylene is an inert material with low surface energy and high chemical stability, which results in poor adhesion to the substrate. Therefore, surface treatments such as oxidation etching can introduce polar groups, increase surface roughness, and thus improve interfacial bonding.

[0009] Furthermore, the modified polyethylene fiber is a polyethylene fiber with polydopamine surface modification, and its preparation method is as follows:

[0010] (1) After ultrasonic treatment of the surface impurities of polyethylene fiber with deionized water, it is dried.

[0011] (2) Prepare a 0.5-2 mol / L persulfate solution (such as ammonium persulfate), add a small amount of acid-base adjuster (such as sulfuric acid or sodium hydroxide) to adjust the pH to 1.5-2.5; add the polyethylene fiber treated in step (1) into it, immerse it at 80-95℃ for 0.5-1h and take it out; after washing and drying, oxidized polyethylene fiber is obtained.

[0012] The surface of polyethylene is selectively oxidized by using the free radical reaction of ammonium persulfate under acidic conditions;

[0013] (3) Add oxidized polyethylene fiber and polydopamine solution with a concentration of 2-5 mg / mL to Tris-HCl buffer solution and mix evenly. After centrifugation at room temperature for 5 min, the precipitate is removed and dried to obtain modified polyethylene fiber.

[0014] By attaching polydopamine to the surface of pretreated oxidized polyethylene fibers to form a dense coating, the wettability of polyethylene fibers is improved. Furthermore, the small polydopamine particles can significantly increase the surface roughness of the oxidized polyethylene fibers, serving as engagement points between the polyethylene fibers and the protective material matrix, thereby enhancing their interfacial bonding performance with the matrix material. Simultaneously, the introduction of amino, hydroxyl, carbon-nitrogen, and carbon-oxygen polar functional groups onto the surface of the polyethylene fibers increases the polarity of the fibers, thereby strengthening the bonding strength with the matrix material.

[0015] Furthermore, the boron-containing compound may be boron carbide powder enriched with B-10 isotope, wherein the abundance of B-10 isotope in the boron carbide powder is not less than 15%.

[0016] Furthermore, in order to improve the dispersibility of boron carbide powder in the system and prevent agglomeration, the boron carbide powder was subjected to surface treatment as follows: after ultrasonic treatment with deionized water, dihydroxyethylaminotrihydroxymethylmethane was added to the boron carbide powder, and ultrasonic treatment was continued at room temperature for 0.5-1.5 h; then hydroxyl-terminated polybutadiene was added to the boron carbide powder, and after stirring at room temperature for 12 h, the powder was washed, centrifuged, and the precipitate was dried in an oven at 50-80℃ to obtain modified boron carbide.

[0017] The significant differences in physicochemical properties between the inorganic filler boron carbide and the surface of the hydrogen-containing resin matrix result in poor dispersibility of boron carbide in the resin matrix, making it prone to agglomeration and thus affecting the overall performance of the material. Therefore, this invention uses hydroxyl-terminated polybutadiene to modify the surface of boron carbide. Hydroxyl-terminated polybutadiene contains a large number of hydroxyl groups and can form hydrogen bonds with boron carbide, adsorbing onto the boron carbide surface and exhibiting good dispersibility, thus enhancing interfacial bonding and improving its dispersibility in the matrix.

[0018] Furthermore, the shielding material includes one or more of the following: bismuth, barium, lanthanum, gadolinium, tantalum, tungsten and / or compounds (such as oxides);

[0019] The present invention also provides a protective material comprising a matrix material and the above-described protective composition, wherein the matrix material is selected from aerogel fiber felt or hydrogen-containing resin, and the protective composition is incorporated into or bonded to the matrix material.

[0020] Furthermore, the aerogel fiber felt is composed of interwoven nanofibers with a porosity greater than 90% and a density less than 0.1 g / cm³. 3 Preferably, the aerogel fiber felt is treated with hydrophobicity to improve its protective performance in humid environments. Specifically, silane reagents (such as trimethylchlorosilane, tetramethoxysilane, chloromethyltrimethylsilane, dimethyldiethoxysilane, methyltrimethoxysilane, and aminopropyltrimethoxysilane) react with the hydroxyl groups on the aerogel surface to form hydrophobic groups (-Si(CH3)3). These hydrophobic groups are then covalently bonded to the aerogel skeleton, resulting in higher stability. The specific treatment method is as follows: the silane reagent is mixed with the aerogel fiber felt at a molar ratio of 1:10-15, and then hydrolyzed in water at 30-50°C for 2 hours, aged, and allowed to stand at room temperature for 1 hour. Finally, it is dried with supercritical carbon dioxide.

[0021] Furthermore, the hydrogen-containing resin is one or more of epoxy resin, hydrogenated epoxy resin, or hydroxyl acrylic resin; it is rich in hydrogen, which can moderate neutrons; it is resistant to gamma-ray irradiation and has high stability; in addition, the hydroxyl groups in the hydroxyl acrylic resin can form hydrogen bonds with the protective composition to improve the overall bonding strength and adhesion.

[0022] Furthermore, the mass ratio of the protective composition to the base material is 1:3 to 1:5.

[0023] The preparation method of the above-mentioned protective material is as follows: after the raw material components of the protective composition are mixed evenly, a dispersion is prepared, which is then coated on the surface of the base material and dried to obtain the protective material.

[0024] The present invention also provides a protective article comprising the above-described protective composition.

[0025] Furthermore, the protective products include protective equipment related to head protection, respiratory protection, eye protection, face protection, hearing protection, hand protection, foot protection, and body protection, such as protective clothing, protective gloves, and protective caps.

[0026] Furthermore, the protective suit is composed of multiple protective layers, consisting of an inner layer, a neutron-absorbing layer, and an outer layer from the inside out; wherein, the neutron-absorbing layer is the aforementioned protective material; the inner layer is a breathable and comfortable layer made of lightweight, highly breathable fabric, with a skin-friendly coating on the fiber surface of the fabric to improve wearing comfort; the outer layer is an abrasion-resistant protective layer made of high-strength, abrasion-resistant, and lightweight synthetic material, with an antistatic coating on the surface of the outer layer.

[0027] Furthermore, the weight of the breathable fabric in the inner layer is 50–100 g / m². 2 .

[0028] Furthermore, the outer layer is a composite fabric of polyimide film and aramid fiber, wherein the thickness of the polyimide film is 0.05-0.1 mm and the content of aramid fiber is 30%-50%.

[0029] The technical solutions of the embodiments of the present invention have at least the following advantages and beneficial effects:

[0030] The protective clothing produced by this invention has excellent protective performance, can effectively shield thermal neutrons, and can form a uniform protective effect on the surface of the protective clothing. It also achieves the advantages of being ultra-lightweight, comfortable, and durable, meeting the diverse needs of workers in neutron radiation environments for protective clothing. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0032] Example 1

[0033] A protective composition, by weight, comprises the following components: 100 parts modified polyethylene fiber, 120 parts modified boron carbide, and 100 parts shielding material; wherein the shielding material comprises: 20 parts each of bismuth oxide powder, barium oxide powder, lanthanum oxide powder, gadolinium oxide powder, and tungsten powder;

[0034] The modified polyethylene fiber is a polyethylene fiber with polydopamine surface modification, and its preparation method is as follows:

[0035] (1) After ultrasonic treatment of the surface impurities of polyethylene fiber with deionized water, it is dried.

[0036] (2) Prepare a 1 mol / L ammonium persulfate solution, add a small amount of sulfuric acid to adjust the pH to 2.0; add the polyethylene fiber treated in step (1) into it, soak it at 85℃ for 1 h and take it out; after washing and drying, oxidized polyethylene fiber is obtained; the solid-liquid ratio of polyethylene fiber to persulfate solution is 1:30 g / mL;

[0037] (3) Mix the oxidized polyethylene fiber and the polydopamine solution with a concentration of 3 mg / mL evenly, centrifuge at room temperature for 5 min, take out the precipitate, and dry it in an oven at 80℃ for 4 h to obtain the modified polyethylene fiber. The solid-liquid ratio of the oxidized polyethylene fiber to the polydopamine solution is 1:80 g / mL.

[0038] The modified boron carbide is hydroxyl-terminated polybutadiene-modified boron carbide powder, and its preparation method is as follows: 5g of boron carbide powder is ultrasonically treated with 500mL of deionized water for 2h, then 1g of dihydroxyethylaminotrihydroxymethylmethane is added, and ultrasonic treatment is continued at room temperature for 1.5h; then 1g of hydroxyl-terminated polybutadiene is added, and the mixture is stirred at room temperature for 12h, washed, centrifuged, and the precipitate is dried in an oven at 60℃ to obtain modified boron carbide.

[0039] Example 2

[0040] The difference between this embodiment and Embodiment 1 is that: a protective composition, by weight, includes the following components: 90 parts of modified polyethylene fiber, 130 parts of modified boron carbide, and 150 parts of shielding material; wherein, the shielding material includes: 30 parts each of bismuth oxide powder, barium oxide powder, lanthanum oxide powder, gadolinium oxide powder, and tungsten powder.

[0041] Example 3

[0042] The difference between this embodiment and Embodiment 1 is that: a protective composition, by weight, includes the following components: 120 parts of modified polyethylene fiber, 100 parts of modified boron carbide, and 100 parts of shielding material; wherein, the shielding material includes: 20 parts each of bismuth oxide powder, barium oxide powder, lanthanum oxide powder, gadolinium oxide powder, and tantalum oxide powder.

[0043] Example 4

[0044] This embodiment provides a protective material, which, by mass ratio, includes aerogel fiber felt in a 1:4 ratio and the protective composition of Example 1; wherein, the aerogel fiber felt is subjected to hydrophobic treatment: trimethylchlorosilane and aerogel fiber felt are mixed at a molar ratio of 1:12, hydrolyzed in water at 40°C for 2 hours, aged at room temperature for 1 hour, and then dried by supercritical carbon dioxide.

[0045] The protective material is prepared by mixing each raw material component of the protective composition of Example 1 with 3 times the mass of deionized water, coating it on the surface of the base material, and drying it in an oven at 90°C for 24 hours; finally, hot pressing it at 80°C and 2MPa for 5 minutes to obtain the protective material.

[0046] Example 5

[0047] This embodiment provides a protective material, which, by mass ratio, comprises a 1:3 aerogel fiber felt and the protective composition of Example 2.

[0048] Example 6

[0049] This embodiment provides a protective material comprising, by mass ratio, 1:5 hydrogenated epoxy resin and the protective composition of Example 3.

[0050] Example 7

[0051] This embodiment provides a protective suit, which consists of an inner layer, a neutron-absorbing layer, and an outer layer from the inside out; wherein, the neutron-absorbing layer is the protective material prepared in Example 4; the thickness ratio of the inner layer, the neutron-absorbing layer, and the outer layer is 1:3:1;

[0052] The inner layer is a breathable and comfortable layer, and its preparation method is as follows: A weight of 70 g / m² is selected. 2 The lightweight and highly breathable ramie fabric is coated with a skin-friendly polydimethylsiloxane coating material by impregnation on the surface of the fabric fibers, and the inner layer material is obtained after drying.

[0053] The outer layer is a wear-resistant protective layer, which is prepared as follows: a polyimide film and aramid fiber are compounded at a mass ratio of 2:1 to obtain a composite material, wherein the thickness of the polyimide film is 0.05 mm, and then an epoxy resin self-leveling antistatic coating is coated on the surface of the composite material to obtain the outer layer material.

[0054] The protective suit is made by sewing the three layers of material together in the order of inner layer, neutron absorption layer and outer layer using a sealing and sewing technique.

[0055] Example 8

[0056] The difference between this embodiment and embodiment 7 is that the neutron absorbing layer is the protective material prepared in embodiment 5.

[0057] Example 9

[0058] The difference between this embodiment and embodiment 7 is that the neutron absorbing layer is the protective material prepared in embodiment 6.

[0059] Comparative Example 1

[0060] The difference between this comparative protective suit and Example 7 is that the polyethylene fiber in the protective composition of the protective material used in the neutron absorbing layer is ordinary polyethylene fiber.

[0061] Comparative Example 2

[0062] The difference between this comparative protective suit and Example 7 is that the boron carbide in the protective composition of the protective material used in the neutron absorbing layer was not modified.

[0063] Experimental Example

[0064] 1. Neutron protection performance tests were conducted on the protective suits prepared in Examples 7-9 and Comparative Examples 1-2: A neutron source was used to simulate the neutron radiation environment. The protective suits prepared in each example and comparative example were placed between the neutron source and the detector, respectively. The neutron flux received by the detector with and without the protective suit was measured, and the protection efficiency was calculated. In the environment surrounding a nuclear power plant, the neutron flux received by the detector without the protective suit was tested to be 35 N / cm². 2 In addition, the thermal neutron flux received by the detector was tested in the environment surrounding the nuclear power plant under protective clothing conditions, and the results are shown in Table 1.

[0065] Table 1 - Test Results of Protection Efficiency

[0066]

[0067]

[0068] As shown in Table 1, the protective clothing prepared by this invention achieved a protection efficiency of over 95% in tests. However, in Comparative Example 1, the lack of modification treatment on the polyethylene fiber resulted in poor interfacial bonding between it and the matrix material, leading to poor interfacial bonding between the modified boron carbide, the shielding material, and the matrix material, thus significantly reducing the protective performance of the resulting protective material. In Comparative Example 2, although the polyethylene fiber was modified, maintaining good interfacial bonding with the matrix material, the lack of modification treatment on the boron carbide resulted in poor dispersion in the system, possibly due to agglomeration. This resulted in poor protective performance of the final protective material, meaning it could not form a uniform protective effect on the matrix surface, leading to a higher neutron throughput.

[0069] The above are merely preferred embodiments of the present invention and are not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A protective composition, characterized in that, By weight, it includes 80-120 parts modified polyethylene fiber, 100-150 parts modified boron-containing compound, and 100-150 parts shielding material. The modified polyethylene fiber is a polyethylene fiber with polydopamine surface modification, and the modified boron-containing compound is a boron-containing compound modified with hydroxyl-terminated polybutadiene.

2. The protective composition according to claim 1, characterized in that, The modified polyethylene fiber is prepared as follows: (1) Polyethylene fibers are ultrasonically treated with deionized water and then dried; (2) Add an acid-base adjuster to the persulfate solution to adjust the pH of the system to 1.5-2.5; add the polyethylene fiber obtained in step (1) into it, soak it for a period of time and then take it out; after washing and drying, oxidized polyethylene fiber is obtained. (3) Mix the oxidized polyethylene fiber and polydopamine solution evenly, centrifuge and remove the precipitate, and dry it to obtain the modified polyethylene fiber.

3. The protective composition according to claim 2, characterized in that, In step (2), the solid-liquid ratio of the polyethylene fiber to the persulfate solution is 1:20-40 g / mL; in step (3), the concentration of the polydopamine solution is 2-5 mg / mL, and the solid-liquid ratio of the oxidized polyethylene fiber to the polydopamine solution is 1:50-100 g / mL.

4. The protective composition according to claim 1, characterized in that, The modified boron-containing compound is a boron carbide powder enriched with B-10 isotope, and the abundance of B-10 isotope in the boron carbide powder is not less than 15%.

5. The protective composition according to claim 4, characterized in that, The modified boron-containing compound is prepared as follows: boron carbide powder is ultrasonically treated with deionized water, then dihydroxyethylaminotrihydroxymethylmethane is added to it, and ultrasonic treatment is continued at room temperature for a period of time; then hydroxyl-terminated polybutadiene is added to it, and after stirring at room temperature, it is washed, centrifuged, the precipitate is taken, dried, and the modified boron carbide is obtained.

6. The protective composition according to claim 4, characterized in that, The mass ratio of boron carbide powder, dihydroxyethylaminotrihydroxymethylmethane, and hydroxyl-terminated polybutadiene is 3-8:1:

1.

7. The protective composition according to claim 1, characterized in that, The shielding material includes one or more of the following: bismuth, barium, lanthanum, gadolinium, tantalum, tungsten and / or their compounds.

8. A protective material, characterized in that, The protective material includes a matrix material and the protective composition according to any one of claims 1-7; The matrix material is aerogel fiber felt or hydrogen-containing resin, and the protective composition is incorporated into or bonded to the matrix material; The mass ratio of the protective composition to the base material is 1:3 to 1:

5.

9. A protective product, characterized in that, The protective article includes the protective composition according to any one of claims 1-7.

10. The protective article according to claim 9, characterized in that, The protective equipment includes protective gear related to head protection, respiratory protection, eye protection, face protection, hearing protection, hand protection, foot protection, and body protection.

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