Neutron shielding material and preparation method thereof

Abstract

The invention relates to the technical field of neutron material shielding, in particular to a neutron shielding material and a preparation method thereof. Specifically, the composite material is prepared from the following components in parts by weight: 64 parts of AFG-90H, 36 parts of DDS, 0.3 part of functionalized MXene, 5 to 20 parts of Sm2O3 / RGO nano compound and 5 to 20 parts of APTES modified Sm2O3. According to the neutron shielding material disclosed by the invention, the components such as AFG-90H, DDS, functionalized MXene, the Sm2O3 / RGO nano-composite and APTES modified Sm2O3 are adopted by optimizing a formula, and an efficient preparation process is combined, so that efficient neutron shielding performance and good mechanical and thermal stability are realized. The simple and feasible preparation method and optimized formula parameters not only reduce the production cost, but also improve the performance of the material, so that the material has wide application prospects in the fields of nuclear facilities, neutron imaging equipment and the like, and has remarkable economic benefits and social benefits.

Description

Technical Field

[0001] The present invention relates to the technical field of neutron material shielding, and in particular to a neutron shielding material and a preparation method thereof. Background Art

[0002] Neutron radiation is not only present in nuclear reactors but also in various industrial, aviation, and radiotherapy fields. Neutrons, which are uncharged, can easily penetrate human tissue and induce ionization, posing a serious threat to human health. Furthermore, neutron radiation can have devastating negative impacts on the lifespan of electronic components and the environment. Consequently, research and development of radiation protection materials, including neutron shielding materials, is extensive in nuclear-related fields.

[0003] To meet the lightweight and high-performance demands of nuclear power plants and facilities, the development of novel neutron shielding materials with superior properties has become an important approach to meet these requirements. For example, combining a hydrogen-rich polymer matrix with high-cross-section neutron-absorbing elements can achieve integrated neutron mitigation and absorption. These materials, such as polyethylene (PE), high-density polyethylene (HDPE), and epoxy resin (EP), have the potential to replace metal and concrete in nuclear facilities.

[0004] In addition, the rare earth element samarium (Sm) is also a suitable neutron absorber with a high natural abundance and a wide neutron absorption spectrum. By connecting the inorganic filler and the organic matrix through a chemical bond "bridge", the dispersion of the filler in the resin matrix can be improved, thereby improving the mechanical properties and neutron shielding effect of the composite material. Too high a filler content will lead to uneven distribution in the polymer matrix and poor interfacial interaction. This defect will reduce the mechanical stability of the epoxy resin (EP) composite material. One of the problems is that it is difficult to achieve high neutron shielding performance and good mechanical properties at the same time, which is usually due to the large difference in physicochemical properties between the inorganic filler and the epoxy resin matrix. Summary of the Invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a neutron shielding material and a preparation method thereof.

[0006] The present invention is achieved through the following technical solutions:

[0007] A neutron shielding material consists of 64 parts by weight of AFG-90H, 36 parts by weight of DDS, 0.3 parts by weight of functionalized MXene, 5 to 20 parts by weight of Sm2O3 / RGO nanocomposite, and 5 to 20 parts by weight of APTES-modified Sm2O3.

[0008] Furthermore, the weight portion of the Sm2O3 / RGO nanocomposite is 5 to 15 parts.

[0009] Furthermore, the weight portion of the APTES-modified Sm2O3 is 5 to 15 parts.

[0010] Furthermore, the weight portion of the Sm2O3 / RGO nanocomposite is 10 parts, and the weight portion of APTES-modified Sm2O3 is 10 parts.

[0011] Furthermore, the synthesis method of the functionalized MXene is:

[0012] 3.2 g LiF was added to 40 mL 9 M HCl, and then 2 g Ti3AlC2 was added in 5 minutes and stirred at room temperature for 24 hours; then centrifuged, the precipitate was washed with deionized water until the pH of the washing solution was about 6, ultrasonically treated for 1 hour after washing, and then centrifuged again; the precipitate was dispersed in 100 mL 1:9 (mass ratio) ethanol water, glacial acetic acid was added under a nitrogen environment to adjust the pH to 3.5, and then AEAPTMS1 g was added dropwise, reacted at room temperature for 2 hours, centrifuged after the reaction was completed, washed with ethanol three times, and vacuum dried at 60 ° C for 24 hours 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 under magnetic stirring for 30 min to form a homogeneous solution. Subsequently, the mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and maintained at 120°C for 3 h. The precipitate was obtained by centrifugation, washed with ethanol and deionized water multiple times, and then dried in air overnight. Finally, it was annealed at 600°C in a muffle furnace for 1 h to obtain Sm2O3.

[0015] 2 g of RGO was ultrasonicated in 100 mL of DMF solution for 0.5 h, 5 g of Sm2O3 was added, ultrasonicated for 1 h, centrifuged, and the precipitate was washed three times with deionized water and dried in vacuum at 60 °C for 24 h to obtain Sm2O3 / RGO nanocomposite materials.

[0016] Furthermore, the synthesis of the 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 under magnetic stirring for 30 min to form a homogeneous solution. Subsequently, the mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and maintained at 120°C for 3 h. The precipitate was obtained by centrifugation, washed with ethanol and deionized water multiple times, and then dried in air overnight. Finally, it was annealed at 600°C in a muffle furnace for 1 h to obtain Sm2O3.

[0018] Sm2O3 and APTES were dispersed in ethanol at a mass ratio of 3:7 for 1 h, centrifuged, washed the precipitate three times with deionized water, and dried in vacuum at 60 °C for 24 h 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: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0020] Step S2: functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 were added to anhydrous ethanol solution, and then the pre-cured resin solution was added, heated to 80°C and ultrasonicated 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 a 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 achieves effective neutron shielding performance and excellent mechanical and thermal stability through an optimized formulation using components such as AFG-90H, DDS, functionalized MXene, Sm2O3 / RGO nanocomposite, and APTES-modified Sm2O3, combined with an efficient preparation process. Its simple preparation method and optimized formulation parameters not only reduce production costs but also improve material performance, promising promising applications in nuclear facilities, neutron imaging equipment, and other fields, with significant economic and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The drawings described herein are used to provide a further understanding of the embodiments of the present invention, constitute a part of this application, and do not constitute a limitation of the embodiments of the present invention.

[0024] Figure 1 is the SEM image of the Sm2O3 / RGO nanocomposite material of the present invention;

[0025] Figure 2 This is the SEM image of APTES modified Sm2O3. DETAILED DESCRIPTION

[0026] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with examples and drawings. The exemplary embodiments of the present invention and their descriptions are only used to explain the present invention and are not intended to limit the present invention.

[0027] In the present invention, AEAPTMS is 3-(2-aminoethyl)aminopropyl]trimethoxysilane; CTAB is hexadecyltrimethylammonium bromide; RGO reduced graphene oxide was purchased from Sigma, product number 777684. DDS is 4,4'-diaminodiphenyl sulfone.

[0028] Synthesis of functionalized MXene in the present invention:

[0029] 3.2 g of LiF was added to 40 mL of 9 M HCl, and then 2 g of Ti3AlC2 was added in 5 minutes and stirred at room temperature for 24 hours; then centrifuged, the precipitate was washed with deionized water until the pH of the washing solution was about 6, and after washing, it was ultrasonically treated for 1 hour and then centrifuged again; the precipitate was dispersed in 100 mL of 1:9 (mass ratio) ethanol water, glacial acetic acid was added under a nitrogen environment to adjust the pH to 3.5, and then AEAPTMS1 g was added dropwise and reacted at room temperature for 2 hours. After the reaction was completed, centrifuged, the precipitate was washed three times with ethanol, and vacuum dried at 60 ° C for 24 hours to obtain functionalized MXene.

[0030] Preparation of Sm2O3 / RGO nanocomposite materials in the present 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 under magnetic stirring for 30 min to form a homogeneous solution. Subsequently, the mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and maintained at 120°C for 3 h. The precipitate was obtained by centrifugation, washed with ethanol and deionized water multiple times, and then dried in air overnight. Finally, it was annealed at 600°C in a muffle furnace for 1 h to obtain Sm2O3.

[0032] 2 g of RGO was ultrasonicated in 100 mL of DMF solution for 0.5 h, 5 g of Sm2O3 was added, ultrasonicated for 1 h, centrifuged, washed with deionized water for three times, and vacuum dried at 60 ° C for 24 h to obtain Sm2O3 / RGO nanocomposite materials. Figure 1 This is the SEM image of the Sm2O3 / RGO nanocomposite material in the present invention.

[0033] Synthesis of APTES-modified Sm2O3 in the present 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 under magnetic stirring for 30 min to form a homogeneous solution. Subsequently, the mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and maintained at 120°C for 3 h. The precipitate was obtained by centrifugation, washed with ethanol and deionized water multiple times, and then dried in air overnight. Finally, it was annealed at 600°C in a muffle furnace for 1 h to obtain Sm2O3.

[0035] Sm2O3 and APTES were dispersed in ethanol at a mass ratio of 3:7 for 1 h, centrifuged, washed with deionized water for three times, and dried in vacuum at 60 °C for 24 h to obtain APTES-modified Sm2O3. Figure 2 This is the SEM image of APTES modified Sm2O3.

[0036] Example 1

[0037] A neutron shielding material consists of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, 5 parts of Sm2O3 / RGO nanocomposite, and 15 parts of APTES-modified Sm2O3 in parts by weight.

[0038] The preparation method of the neutron shielding material is as follows:

[0039] Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0040] Step S2: functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 were added to anhydrous ethanol solution, and then the pre-cured resin solution was added, heated to 80°C and ultrasonicated 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 a neutron shielding material.

[0041] Example 2

[0042] A neutron shielding material consists of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, 10 parts of Sm2O3 / RGO nanocomposite, and 10 parts of APTES-modified Sm2O3 in parts by weight.

[0043] The preparation method of the neutron shielding material is as follows:

[0044] Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0045] Step S2: functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 were added to anhydrous ethanol solution, and then the pre-cured resin solution was added, heated to 80°C and ultrasonicated 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 a neutron shielding material.

[0046] Example 3

[0047] A neutron shielding material consists of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, 15 parts of Sm2O3 / RGO nanocomposite, and 5 parts of APTES-modified Sm2O3 in parts by weight.

[0048] The preparation method of the neutron shielding material is as follows:

[0049] Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0050] Step S2: functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 were added to anhydrous ethanol solution, and then the pre-cured resin solution was added, heated to 80°C and ultrasonicated 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 a neutron shielding material.

[0051] Comparative Example 1

[0052] A neutron shielding material consists of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, and 20 parts of Sm2O3 in parts by weight.

[0053] The preparation method of the neutron shielding material is as follows:

[0054] Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0055] Step S2: Add functionalized MXene and Sm2O3 to an anhydrous ethanol solution, then add the pre-cured resin solution, heat to 80°C and ultrasonicate for 1 hour, pour into a mold for vacuum degassing, cure at 85°C for 3 hours, and then cool to room temperature to obtain a neutron shielding material.

[0056] Comparative Example 2

[0057] A neutron shielding material consists of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, and 20 parts of APTES-modified Sm2O3, by weight.

[0058] The preparation method of the neutron shielding material is as follows:

[0059] Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0060] Step S2: Add functionalized MXene and APTES-modified Sm2O3 to anhydrous ethanol solution, then add pre-cured resin solution, heat to 80°C and ultrasonicate for 1 hour, pour into a mold for vacuum degassing, cure at 85°C for 3 hours, and then cool to room temperature to obtain a neutron shielding material.

[0061] Comparative Example 3

[0062] A neutron shielding material consists of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, and 15 parts of APTES-modified Sm2O3, by weight.

[0063] The preparation method of the neutron shielding material is as follows:

[0064] Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0065] Step S2: Add functionalized MXene and APTES-modified Sm2O3 to anhydrous ethanol solution, then add pre-cured resin solution, heat to 80°C and ultrasonicate for 1 hour, pour into a mold for vacuum degassing, cure at 85°C for 3 hours, and then cool to room temperature to obtain a neutron shielding material.

[0066] Comparative Example 4

[0067] A neutron shielding material consists of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, and 5 parts of Sm2O3 / RGO nanocomposite in parts by weight.

[0068] The preparation method of the neutron shielding material is as follows:

[0069] Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0070] Step S2: functionalized MXene and Sm2O3 / RGO nanocomposites were added to anhydrous ethanol solution, followed by the addition of pre-cured resin solution, heated to 80°C and ultrasonicated 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 a neutron shielding material.

[0071] Comparative Example 5

[0072] A neutron shielding material consists of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, and 20 parts of Sm2O3 / RGO nanocomposite in parts by weight.

[0073] The preparation method of the neutron shielding material is as follows:

[0074] Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution;

[0075] Step S2: functionalized MXene and Sm2O3 / RGO nanocomposites were added to anhydrous ethanol solution, followed by the addition of pre-cured resin solution, heated to 80°C and ultrasonicated 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 a neutron shielding material.

[0076] Test Case

[0077] Mechanical properties are tested according to GB / T 2567-2021. Impact test: pendulum impact velocity is 2.9m / 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 can be seen from Table 1, Examples 1 to 3 (a combination of Sm2O3 / RGO nanocomposites and APTES-modified Sm2O3) perform significantly better than Comparative Example 1 and Comparative Example 5 (containing only one of Sm2O3 / RGO nanocomposites or APTES-modified Sm2O3) in terms of impact strength and tensile strength. Specifically, the impact strength of Example 1 is 29.14 J / m and the tensile strength is 31.14 MPa; the impact strength of Example 2 is 33.14 J / m and the tensile strength is 35.64 MPa; the impact strength of Example 3 is 31.12 J / m and the tensile strength is 32.62 MPa. The impact strength of Comparative Example 1 is only 18.24 J / m and the tensile strength is 24.01 MPa; the impact strength of Comparative Example 5 is 23.25 J / m and the tensile strength is 29.12 MPa. This demonstrates that the combination of Sm2O3 / RGO nanocomposites and APTES-modified Sm2O3 significantly improves the mechanical properties of the material. In terms of neutron transmittance, Examples 1-3 achieved 13.2%, 9.8%, and 14.1%, respectively, while Comparative Examples 1 and 5 achieved 9.7% and 26.2%, respectively. Example 2 had the lowest neutron transmittance, indicating the best neutron shielding effect, while Comparative Example 5 had the highest neutron transmittance, indicating a relatively poor shielding effect.

[0080] In summary, the combination of Sm2O3 / RGO nanocomposites and APTES-modified Sm2O3 has significant advantages in improving the impact strength and tensile strength of the material, and also shows good effects on neutron shielding performance.

[0081] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method 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 in the scope of protection of the present invention.

Claims

1. A neutron shielding material, characterized in that: The composition is composed of 64 parts of AFG-90H, 36 parts of DDS, 0.3 parts of functionalized MXene, 5 to 20 parts of Sm2O3 / RGO nanocomposite, and 5 to 20 parts of APTES-modified Sm2O3 by weight.

2. The neutron shielding material according to claim 1, wherein The weight portion of the Sm2O3 / RGO nanocomposite is 5 to 15 parts.

3. The neutron shielding material according to claim 2, characterized in that The weight portion of the APTES modified Sm2O3 is 5 to 15 parts.

4. The neutron shielding material according to claim 3, wherein: The weight portion of the Sm2O3 / RGO nanocomposite is 10 parts, and the weight portion of APTES-modified Sm2O3 is 10 parts.

5. The neutron shielding material according to claim 4, characterized in that The synthesis method of the functionalized MXene is: 3.2 g of LiF was added to 40 mL of 9 M HCl, and then 2 g of Ti3AlC2 was added in 5 minutes and stirred at room temperature for 24 hours; then centrifuged, the precipitate was washed with deionized water until the pH of the washing solution was about 6, and after washing, it was ultrasonically treated for 1 hour and then centrifuged again; the precipitate was dispersed in 100 mL of ethanol water, glacial acetic acid was added under a nitrogen environment to adjust the pH to 3.5, and then AEAPTMS1 g was added dropwise and reacted at room temperature for 2 hours. After the reaction was completed, centrifuged, the precipitate was washed three times with ethanol, and vacuum dried at 60 ° C for 24 hours to obtain functionalized MXene.

6. The neutron shielding material according to claim 4, characterized in that 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 min to form a homogeneous solution. Subsequently, the mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and maintained at 120 °C for 3 h. The precipitate was obtained by centrifugation, washed with ethanol and deionized water several times, and then dried in air overnight; finally, it was annealed at 600 °C in a muffle furnace for 1 hour to obtain Sm2O3; 2 g of RGO was ultrasonicated in 100 mL of DMF solution for 0.5 h, 5 g of Sm2O3 was added, ultrasonicated for 1 h, centrifuged, and the precipitate was washed three times with deionized water and dried in vacuum at 60 °C for 24 h to obtain Sm2O3 / RGO nanocomposite materials.

7. The neutron shielding material according to claim 4, characterized in that The synthesis of the APTES-modified Sm2O3 is as follows: 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 min to form a homogeneous solution. Subsequently, the mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and maintained at 120 °C for 3 h. The precipitate was obtained by centrifugation, washed with ethanol and deionized water several times, and then dried in air overnight; finally, it was annealed at 600 °C in a muffle furnace for 1 hour to obtain Sm2O3; Sm2O3 and APTES were dispersed in ethanol at a mass ratio of 3:7 for 1 h, centrifuged, washed the precipitate three times with deionized water, and dried in vacuum at 60 °C for 24 h to obtain APTES-modified Sm2O3.

8. The method for preparing a neutron shielding material according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step S1: mixing AFG-90H and DDS to obtain a pre-cured resin solution; Step S2: functionalized MXene, Sm2O3 / RGO nanocomposite and APTES-modified Sm2O3 were added to anhydrous ethanol solution, and then the pre-cured resin solution was added, heated to 80°C and ultrasonicated 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 a neutron shielding material.

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