Neutron shielding material and method of making same
By optimizing the formulation and preparation process of neutron shielding materials, and combining AFG-90H, DDS, functionalized MXene, Sm2O3/RGO nanocomposite and APTES-modified Sm2O3, the contradiction between mechanical properties and shielding effect of neutron shielding materials was resolved, achieving high-efficiency neutron shielding performance and good mechanical stability, reducing production costs, and broadening the application fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CNOOC CHANGZHOU PAINT & COATINGS IND RES INST
- Filing Date
- 2025-06-19
- Publication Date
- 2026-06-02
AI Technical Summary
Existing neutron shielding materials cannot simultaneously achieve high mechanical properties and good neutron shielding effects, especially due to the significant differences in physicochemical properties between inorganic fillers and organic matrices.
Neutron shielding materials were formed by using components such as AFG-90H, DDS, functionalized MXene, Sm2O3/RGO nanocomposite and APTES-modified Sm2O3, and by optimizing the formulation and preparation process. This included mixing these components in anhydrous ethanol and curing them at a specific temperature.
It achieves efficient neutron shielding performance, good mechanical and thermal stability, reduces production costs, and broadens its application prospects in fields such as nuclear facilities and neutron imaging equipment.
Smart Images
Figure CN120484444B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of neutron material shielding technology, and in particular to a neutron shielding material and its preparation method. Background Technology
[0002] Neutron radiation is not only present in nuclear reactors but also widely found in various industrial, aerospace, and radiotherapy fields. Uncharged neutrons can easily penetrate human tissue and cause ionization, posing a serious threat to human health. Furthermore, neutron radiation can have fatal negative impacts on the lifespan of electronic components and the environment. Therefore, in nuclear-related fields, the research and development of radiation protection materials, including neutron shielding materials, is extensive.
[0003] To meet the demands of nuclear power plants and facilities for lightweighting and high performance, developing novel neutron shielding materials with superior properties has become an important approach to fulfilling neutron protection requirements. For example, mixing hydrogen-rich polymer matrices with high-cross-section neutron-absorbing elements can integrate neutron mitigation and absorption. These materials, such as polyethylene (PE), high-density polyethylene (HDPE), and epoxy resin (EP), hold promise as alternatives to metals and concrete in nuclear facilities.
[0004] Furthermore, samarium (Sm), a rare earth element, is also a suitable neutron absorber, possessing high natural abundance and a broad neutron absorption spectrum. Connecting inorganic fillers and the organic matrix through chemical bonds can improve the dispersibility of the filler in the resin matrix, thereby enhancing the mechanical properties and neutron shielding effect of the composite material. Excessive filler content leads to uneven distribution within the polymer matrix and poor interfacial interactions, which reduces the mechanical stability of epoxy (EP) composites. One challenge is achieving both high neutron shielding performance and good mechanical properties simultaneously, typically due to significant differences in the physicochemical properties between the inorganic filler and the epoxy resin matrix. Summary of the Invention
[0005] To address the problems existing in the prior art, this invention provides a neutron shielding material and its preparation method.
[0006] This invention is achieved through the following technical solution:
[0007] A neutron shielding material, by weight, is composed of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, 5 to 20 parts Sm2O3 / RGO nanocomposite, and 5 to 20 parts APTES-modified Sm2O3.
[0008] Furthermore, the Sm2O3 / RGO nanocomposite comprises 5 to 15 parts by weight.
[0009] Furthermore, the APTES-modified Sm2O3 comprises 5 to 15 parts by weight.
[0010] Furthermore, the Sm2O3 / RGO nanocomposite comprises 10 parts by weight, and the APTES-modified Sm2O3 comprises 10 parts by weight.
[0011] Furthermore, the method for synthesizing the functionalized MXene is as follows:
[0012] 3.2 g LiF was added to 40 mL of 9 M HCl, followed by 2 g Ti3AlC2 over 5 min. The mixture was stirred at room temperature for 24 h. After centrifugation, the precipitate was washed with deionized water until the pH of the washing solution was approximately 6. After washing, the mixture was sonicated for 1 h and then centrifuged again. The precipitate was dispersed in 100 mL of 1:9 (mass ratio) ethanol-water mixture. Glacial acetic acid was added under nitrogen atmosphere to adjust the pH to 3.5. Then, 1 g of AEAPTMS was added dropwise. The mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times with ethanol. The mixture was then dried under vacuum at 60 °C for 24 h to obtain functionalized MXene.
[0013] Furthermore, the preparation of the Sm2O3 / RGO nanocomposite material:
[0014] 0.84 g of Sm(NO3)3·6H2O, 100 mg of CTAB, and 400 mg of KOH were dissolved in 60 mL of deionized water and stirred magnetically for 30 minutes to form a homogeneous solution. The solution was then transferred to a 100 mL PTFE-lined stainless steel autoclave and kept at 120 °C for 3 hours. The precipitate was obtained by centrifugation, washed repeatedly with ethanol and deionized water, and then dried in air overnight. Finally, the precipitate was annealed in a muffle furnace at 600 °C for 1 hour to obtain Sm2O3.
[0015] 2g of RGO was sonicated in 100mL of DMF solution for 0.5h, 5g of Sm2O3 was added, and the mixture was sonicated for 1h. After centrifugation, the precipitate was washed three times with deionized water and dried under vacuum at 60℃ for 24h to obtain the Sm2O3 / RGO nanocomposite material.
[0016] Furthermore, the synthesis of APTES-modified Sm2O3 is as follows:
[0017] 0.84 g of Sm(NO3)3·6H2O, 100 mg of CTAB, and 400 mg of KOH were dissolved in 60 mL of deionized water and stirred magnetically for 30 minutes to form a homogeneous solution. The solution was then transferred to a 100 mL PTFE-lined stainless steel autoclave and kept at 120 °C for 3 hours. The precipitate was obtained by centrifugation, washed repeatedly with ethanol and deionized water, and then air-dried overnight. Finally, it was annealed in a muffle furnace at 600 °C for 1 hour to obtain Sm2O3.
[0018] Sm2O3 and APTES were dispersed in ethanol at a mass ratio of 3:7. After 1 hour, the mixture was centrifuged, the precipitate was washed three times with deionized water, and then dried under vacuum at 60°C for 24 hours to obtain APTES-modified Sm2O3.
[0019] The present invention also provides a method for preparing a neutron shielding material, comprising the following steps: Step S1: AFG-90H and DDS are mixed to obtain a pre-cured resin solution;
[0020] Step S2: Functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 are added to anhydrous ethanol solution, then a pre-cured resin solution is added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0021] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0022] The neutron shielding material of this invention, through optimized formulation and the use of AFG-90H, DDS, functionalized MXene, Sm2O3 / RGO nanocomposite, and APTES-modified Sm2O3, combined with an efficient preparation process, achieves high-performance neutron shielding and excellent mechanical and thermal stability. Its simple and easy-to-implement preparation method and optimized formulation parameters not only reduce production costs but also improve material performance, making it promising for applications in nuclear facilities, neutron imaging equipment, and other fields, with significant economic and social benefits. Attached Figure Description
[0023] The accompanying drawings, which are included to provide a further understanding of the embodiments of the present invention and form part of this application, are not intended to limit the embodiments of the present invention.
[0024] Figure 1 Here is a SEM image of the Sm2O3 / RGO nanocomposite material in this invention;
[0025] Figure 2 SEM image of Sm2O3 modified with APTES. Detailed Implementation
[0026] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments and accompanying drawings. The illustrative embodiments and descriptions of the present invention are only used to explain the present invention and are not intended to limit the present invention.
[0027] In this invention, AEAPTMS is 3-(2-aminoethyl)aminopropyltrimethoxysilane; CTAB is hexadecyltrimethylammonium bromide; RGO reduced graphene oxide was purchased from Sigma, catalog number 777684; and DDS is 4,4'-diaminodiphenyl sulfone.
[0028] Synthesis of functionalized MXene in this invention:
[0029] Add 3.2 g LiF to 40 mL of 9 M HCl, then add 2 g Ti3AlC2 over 5 min and stir at room temperature for 24 h. Centrifuge and wash the precipitate with deionized water until the pH of the washing solution is about 6. After washing, sonicate for 1 h and centrifuge again. Disperse the precipitate in 100 mL of 1:9 (mass ratio) ethanol-water mixture, adjust the pH to 3.5 by adding glacial acetic acid under nitrogen atmosphere, then add 1 g of AEAPTMS dropwise and react at room temperature for 2 h. After the reaction is complete, centrifuge, wash the precipitate three times with ethanol, and dry under vacuum at 60 °C for 24 h to obtain functionalized MXene.
[0030] Preparation of Sm2O3 / RGO nanocomposite material in this invention:
[0031] 0.84 g of Sm(NO3)3·6H2O, 100 mg of CTAB, and 400 mg of KOH were dissolved in 60 mL of deionized water and stirred magnetically for 30 minutes to form a homogeneous solution. The solution was then transferred to a 100 mL PTFE-lined stainless steel autoclave and kept at 120 °C for 3 hours. The precipitate was obtained by centrifugation, washed repeatedly with ethanol and deionized water, and then dried in air overnight. Finally, the precipitate was annealed in a muffle furnace at 600 °C for 1 hour to obtain Sm2O3.
[0032] 2 g of RGO was sonicated in 100 mL of DMF solution for 0.5 h, then 5 g of Sm2O3 was added, and the mixture was sonicated for 1 h. After centrifugation, the precipitate was washed three times with deionized water and dried under vacuum at 60 °C for 24 h to obtain the Sm2O3 / RGO nanocomposite material. Figure 1 This is a SEM image of the Sm2O3 / RGO nanocomposite material in this invention.
[0033] Synthesis of APTES-modified Sm2O3 in this invention
[0034] 0.84 g of Sm(NO3)3·6H2O, 100 mg of CTAB, and 400 mg of KOH were dissolved in 60 mL of deionized water and stirred magnetically for 30 minutes to form a homogeneous solution. The solution was then transferred to a 100 mL PTFE-lined stainless steel autoclave and kept at 120 °C for 3 hours. The precipitate was obtained by centrifugation, washed repeatedly with ethanol and deionized water, and then air-dried overnight. Finally, it was annealed in a muffle furnace at 600 °C for 1 hour to obtain Sm2O3.
[0035] Sm₂O₃ and APTES were dispersed in ethanol at a mass ratio of 3:7. After 1 hour, the mixture was centrifuged, the precipitate was washed three times with deionized water, and then dried under vacuum at 60°C for 24 hours to obtain APTES-modified Sm₂O₃. Figure 2 SEM image of Sm2O3 modified with APTES.
[0036] Example 1
[0037] A neutron shielding material, by weight, consists of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, 5 parts Sm2O3 / RGO nanocomposite, and 15 parts APTES-modified Sm2O3.
[0038] The preparation method of the neutron shielding material is as follows:
[0039] Step S1: Mix AFG-90H and DDS to obtain a pre-cured resin solution;
[0040] Step S2: Functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 are added to anhydrous ethanol solution, then a pre-cured resin solution is added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0041] Example 2
[0042] A neutron shielding material, by weight, consists of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, 10 parts Sm2O3 / RGO nanocomposite, and 10 parts APTES-modified Sm2O3.
[0043] The preparation method of the neutron shielding material is as follows:
[0044] Step S1: Mix AFG-90H and DDS to obtain a pre-cured resin solution;
[0045] Step S2: Functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 are added to anhydrous ethanol solution, then a pre-cured resin solution is added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0046] Example 3
[0047] A neutron shielding material, by weight, consists of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, 15 parts Sm2O3 / RGO nanocomposite, and 5 parts APTES-modified Sm2O3.
[0048] The preparation method of the neutron shielding material is as follows:
[0049] Step S1: Mix AFG-90H and DDS to obtain a pre-cured resin solution;
[0050] Step S2: Functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 are added to anhydrous ethanol solution, then a pre-cured resin solution is added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0051] Comparative Example 1
[0052] A neutron shielding material, by weight, is composed of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, and 20 parts Sm2O3.
[0053] The preparation method of the neutron shielding material is as follows:
[0054] Step S1: Mix AFG-90H and DDS to obtain a pre-cured resin solution;
[0055] Step S2: Functionalized MXene and Sm2O3 are added to anhydrous ethanol solution, then pre-cured resin solution is added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0056] Comparative Example 2
[0057] A neutron shielding material, by weight, is composed of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, and 20 parts APTES-modified Sm2O3.
[0058] The preparation method of the neutron shielding material is as follows:
[0059] Step S1: Mix AFG-90H and DDS to obtain a pre-cured resin solution;
[0060] Step S2: Functionalized MXene and APTES-modified Sm2O3 are added to anhydrous ethanol solution, then a pre-cured resin solution is added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0061] Comparative Example 3
[0062] A neutron shielding material, by weight, is composed of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, and 15 parts APTES-modified Sm2O3.
[0063] The preparation method of the neutron shielding material is as follows:
[0064] Step S1: Mix AFG-90H and DDS to obtain a pre-cured resin solution;
[0065] Step S2: Functionalized MXene and APTES-modified Sm2O3 are added to anhydrous ethanol solution, then a pre-cured resin solution is added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0066] Comparative Example 4
[0067] A neutron shielding material, by weight, is composed of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, and 5 parts Sm2O3 / RGO nanocomposite.
[0068] The preparation method of the neutron shielding material is as follows:
[0069] Step S1: Mix AFG-90H and DDS to obtain a pre-cured resin solution;
[0070] Step S2: Functionalized MXene and Sm2O3 / RGO nanocomposite were added to anhydrous ethanol solution, then a pre-cured resin solution was added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0071] Comparative Example 5
[0072] A neutron shielding material, by weight, is composed of 64 parts AFG-90H, 36 parts DDS, 0.3 parts functionalized MXene, and 20 parts Sm2O3 / RGO nanocomposite.
[0073] The preparation method of the neutron shielding material is as follows:
[0074] Step S1: Mix AFG-90H and DDS to obtain a pre-cured resin solution;
[0075] Step S2: Functionalized MXene and Sm2O3 / RGO nanocomposite were added to anhydrous ethanol solution, then a pre-cured resin solution was added, heated to 80°C and sonicated for 1 hour, poured into a mold for vacuum degassing, cured at 85°C for 3 hours, and then cooled to room temperature to obtain neutron shielding material.
[0076] Test case
[0077] Mechanical properties were tested according to GB / T 2567-2021. Impact test: pendulum impact velocity 2.9 m / s.
[0078] Impact strength (J / m) Tensile strength / MPa Neutron transmittance / % Example 1 29.14 31.14 13.2 Example 2 33.14 35.64 9.8 Example 3 31.12 32.62 14.1 Comparative Example 1 18.24 24.01 9.7 Comparative Example 2 24.24 27.26 20.1 Comparative Example 3 22.24 25.24 22.3 Comparative Example 4 19.15 25.67 21.3 Comparative Example 5 23.25 29.12 26.2
[0079] As shown in Table 1, Examples 1-3 (combinations of Sm₂O₃ / RGO nanocomposites and APTES-modified Sm₂O₃) exhibited significantly better impact strength and tensile strength than Comparative Examples 1 and 5 (containing only one of Sm₂O₃ / RGO nanocomposites or APTES-modified Sm₂O₃). Specifically, Example 1 showed an impact strength of 29.14 J / m and a tensile strength of 31.14 MPa; Example 2 showed an impact strength of 33.14 J / m and a tensile strength of 35.64 MPa; and Example 3 showed an impact strength of 31.12 J / m and a tensile strength of 32.62 MPa. In contrast, Comparative Example 1 showed an impact strength of only 18.24 J / m and a tensile strength of 24.01 MPa; and Comparative Example 5 showed an impact strength of 23.25 J / m and a tensile strength of 29.12 MPa. This indicates that the combination of Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 can significantly improve the mechanical properties of the material. Regarding neutron transmittance, the neutron transmittances of Examples 1-3 were 13.2%, 9.8%, and 14.1%, respectively, while those of Comparative Examples 1 and 5 were 9.7% and 26.2%, respectively. Example 2 had the lowest neutron transmittance, indicating its best neutron shielding effect, while Comparative Example 5 had the highest neutron transmittance, indicating its relatively poor shielding effect.
[0080] In summary, the combination of Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 has significant advantages in improving the impact strength and tensile strength of the material, while also showing good performance in neutron shielding.
[0081] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. 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 neutron shielding material, characterized in that, 64 parts by weight of AFG Composition: 90H, 36 parts DDS, 0.3 parts functionalized MXene, 5 to 20 parts Sm2O3 / RGO nanocomposite, 5 to 20 parts APTES modified Sm2O3; Preparation of the Sm2O3 / RGO nanocomposite material: 0.84 g of Sm(NO3)3·6H2O, 100 mg of CTAB and 400 mg of KOH were dissolved in 60 mL of deionized water and stirred under magnetic stirring for 30 minutes to form a homogeneous solution; then, the mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and kept at 120 °C for 3 h. The precipitate was obtained by centrifugation, washed repeatedly with ethanol and deionized water, and then dried in air overnight. Finally, it was annealed in a muffle furnace at 600℃ for 1 hour to obtain Sm2O3. 2g of RGO was sonicated in 100mL of DMF solution for 0.5h, 5g of Sm2O3 was added, and the mixture was sonicated for 1h. After centrifugation, the precipitate was washed three times with deionized water and dried under vacuum at 60℃ for 24h to obtain the Sm2O3 / RGO nanocomposite material. The synthesis of APTES-modified Sm2O3 is as follows: 0.84 g of Sm(NO3)3·6H2O, 100 mg of CTAB and 400 mg of KOH are dissolved in 60 mL of deionized water and stirred under magnetic stirring for 30 minutes to form a homogeneous solution; then, the mixed solution is transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and kept at 120 °C for 3 h. The precipitate was obtained by centrifugation, washed repeatedly with ethanol and deionized water, and then dried in air overnight. Finally, it was annealed in a muffle furnace at 600°C for 1 hour to obtain Sm2O3. Sm2O3 and APTES were dispersed in ethanol at a mass ratio of 3:7, centrifuged for 1 hour, washed three times with deionized water, and dried under vacuum at 60°C for 24 hours to obtain APTES-modified Sm2O3.
2. The neutron shielding material as described in claim 1, characterized in that, The Sm2O3 / RGO nanocomposite is present in 5 to 15 parts by weight.
3. The neutron shielding material as described in claim 2, characterized in that, The APTES-modified Sm2O3 is present in 5 to 15 parts by weight.
4. The neutron shielding material as described in claim 3, characterized in that, The Sm2O3 / RGO nanocomposite comprises 10 parts by weight, and the APTES-modified Sm2O3 comprises 10 parts by weight.
5. The neutron shielding material as described in claim 1, characterized in that, The method for synthesizing the functionalized MXene is as follows: 3.2 g LiF was added to 40 mL of 9 M HCl, and then 2 g Ti3AlC2 was added over 5 min. The mixture was stirred at room temperature for 24 h. After centrifugation, the precipitate was washed with deionized water until the pH of the washing solution was 6. After washing, the mixture was sonicated for 1 h and then centrifuged again. The precipitate was dispersed in 100 mL of an ethanol-water solution with a mass ratio of 1:
9. Glacial acetic acid was added under nitrogen atmosphere to adjust the pH to 3.
5. Then, 1 g of AEAPTMS was added dropwise and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was centrifuged, and the precipitate was washed three times with ethanol. The mixture was then dried under vacuum at 60 °C for 24 h to obtain the functionalized MXene.
6. The method for preparing the neutron shielding material according to any one of claims 1 to 5, characterized in that, Includes the following steps: Step S1 will AFG 90H and DDS are mixed to obtain a pre-cured resin solution; Step S2: Functionalized MXene, Sm2O3 / RGO nanocomposite and APTES modified Sm2O3 are added to anhydrous ethanol solution, then the pre-cured resin solution is added, heated to 80℃ and then sonicated for 1h, poured into a mold for vacuum degassing, cured at 85℃ for 3h, and then cooled to room temperature to obtain neutron shielding material.