A flexible anti-radiation material, a preparation method and application thereof

Abstract

The application relates to the technical field of high polymer materials, and discloses a flexible anti-radiation material, a preparation method and application thereof, the flexible anti-radiation material comprising an anti-radiation polymer layer and an anti-radiation particle layer arranged on the anti-radiation polymer layer; components of the anti-radiation particle layer include anti-radiation glass particles and a binder; components of the anti-radiation polymer layer include silicone rubber and nano AZO powder; the anti-radiation glass particles are composed of the following components in mass percentage: SiO 2 70%~83%、B2O3 3%~8%、Li2O 2.5%~7%、CeO2 2%~7%、WO3 1%~3%、MoO3 1%~2%、Bi2O3 1.6%~3.3%。Through the technical scheme, the problem that the anti-radiation property and the anti-radiation stability of the anti-radiation material in the prior art are poor is solved.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a flexible radiation-resistant material, its preparation method, and its application. Background Technology

[0002] As a protective layer for batteries, battery protective covers have high requirements for radiation protection performance, optical performance, and mechanical performance. Especially with the development of solar power generation in space, traditional rigid glass protective covers have shortcomings such as heavy weight and large folded volume. Glass protective cover materials are gradually developing towards flexibility. However, existing flexible protective cover materials still have poor radiation resistance, and their radiation resistance decreases significantly after radiation exposure, resulting in insufficient radiation resistance stability.

[0003] Therefore, developing a flexible radiation-resistant material with excellent radiation resistance and stability will be of great significance for broadening its application in fields such as space battery protection and the development of radiation-resistant materials. Summary of the Invention

[0004] This invention proposes a flexible radiation-resistant material, its preparation method, and its application, which solves the problem of poor radiation resistance and radiation stability of radiation-resistant materials in related technologies.

[0005] The technical solution of the present invention is as follows:

[0006] This invention proposes a flexible radiation-resistant material, comprising a radiation-resistant polymer layer and a radiation-resistant particle layer disposed on the radiation-resistant polymer layer;

[0007] The components of the radiation-resistant particle layer include radiation-resistant glass particles and a binder;

[0008] The components of the radiation-resistant polymer layer include silicone rubber and nano-AZO powder;

[0009] The radiation-resistant glass particles are composed of the following components by mass percentage: SiO2 70%~83%, B2O3 3%~8%, Li2O 2.5%~7%, CeO2 2%~7%, WO3 1%~3%, MoO3 1%~2%, Bi2O3 1.6%~3.3%.

[0010] As a further technical solution, the adhesive includes a SEBS solution.

[0011] As a further technical solution, the radiation-resistant glass particles are composed of the following components by mass percentage: SiO2 70%~83%, B2O3 3%~8%, Li2O 2.5%~7%, CeO2 2%~7%, WO3 1%~3%, MoO3 1%~2%, Bi2O3 1.6%~3.3%, Er2O3 1%~3%, and Ta2O5 1%~1.5%.

[0012] In this invention, by introducing Er2O3 and Ta2O5 into the radiation-resistant glass particle component of the radiation-resistant particle layer, and working synergistically with CeO2, the radiation resistance and radiation stability of the radiation-resistant material are further improved.

[0013] As a further technical solution, the radiation-resistant glass particles are composed of the following components by mass percentage: SiO2 70%~83%, B2O3 3%~8%, Li2O 2.5%~7%, CeO2 2%~7%, WO3 1%~3%, MoO3 1%~2%, Bi2O3 1.6%~3.3%, Er2O3 1%~3%, Ta2O5 1%~1.5%, and 6%≤CeO2+Er2O3+Ta2O5≤10%.

[0014] In this invention, by limiting the mass percentage content of CeO2, Er2O3 and Ta2O5 in the components of the radiation-resistant glass particles to 6%≤CeO2+Er2O3+Ta2O5≤10%, the radiation resistance and radiation stability of the radiation-resistant material are further improved.

[0015] As a further technical solution, the radiation-resistant glass particles are composed of the following components by mass percentage: SiO2 70%~83%, B2O3 3%~8%, Li2O 2.5%~7%, CeO2 2%~7%, WO3 1%~3%, MoO3 1%~2%, Bi2O3 1.6%~3.3%, Er2O3 1%~3%, Ta2O5 1%~1.5%, and 7.5%≤CeO2+Er2O3+Ta2O5≤8.7%.

[0016] In this invention, by limiting the mass percentage content of CeO2, Er2O3 and Ta2O5 in the components of the radiation-resistant glass particles to 7.5%≤CeO2+Er2O3+Ta2O5≤8.7%, the radiation resistance and radiation stability of the radiation-resistant material are further improved.

[0017] As a further technical solution, the method for preparing the radiation-resistant glass particles includes the following steps:

[0018] A1. Weigh the raw materials according to the composition of the radiation-resistant glass particles, then melt and mix them, and quench them in water to obtain crude radiation-resistant glass particles.

[0019] A2. The crude anti-radiation glass particles are post-processed to obtain anti-radiation glass particles with a particle size of 10~25μm.

[0020] As a further technical solution, the post-processing involves first pressurizing to 8-12 MPa and then depressurizing to 0.08-0.13 MPa for pulverization.

[0021] As a further technical solution, in step A1, a clarifying agent is added after the melt mixing for clarification treatment; the clarifying agent consists of SnO2 and Sb2O3; the mass of the clarifying agent accounts for 1% to 2.5% of the mass of the raw materials.

[0022] As a further technical solution, the thickness of the radiation-resistant polymer layer is 50~100μm; the thickness of the radiation-resistant particle layer is 10~25μm.

[0023] This invention also proposes a method for preparing the aforementioned flexible radiation-resistant material, comprising the following steps:

[0024] S1. Mix the radiation-resistant glass particles and the binder to obtain a mixture;

[0025] S2. The components of the radiation-resistant polymer layer are coated onto the surface of the target substrate to obtain the radiation-resistant polymer layer;

[0026] S3. Coat the mixture onto the upper surface of the radiation-resistant polymer layer to obtain a flexible radiation-resistant material.

[0027] As a further technical solution, the coating temperature in step S2 is 130~180℃, and the curing time after coating is 120~900s.

[0028] As a further technical solution, the coating temperature in step S3 is 150~190℃, and the curing time after coating is 60~240s.

[0029] The present invention also proposes the application of the flexible radiation-resistant material or the flexible radiation-resistant material prepared by the aforementioned method in the protection of space batteries.

[0030] The working principle and beneficial effects of this invention are as follows:

[0031] In this invention, the radiation-resistant material adopts a double-layer structure. Through the synergistic effect between the radiation-resistant particle layer and the radiation-resistant polymer layer, the radiation resistance and radiation stability of the radiation-resistant material are significantly improved. At the same time, the obtained radiation-resistant material has excellent flexibility. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] In the following examples and comparative examples, the nano AZO powder was of type JC-J50L with a particle size of 50nm, purchased from Kumar Amin Export Company; the silicone rubber was of type KL-2055AB, purchased from Shenzhen Kanglibang Technology Co., Ltd.; the SEBS solution was prepared by dissolving SEBS of type G1654 in cyclohexane, wherein the mass-volume ratio of SEBS to cyclohexane was 1g:10mL.

[0034] Example 1

[0035] The flexible radiation-resistant material includes a radiation-resistant polymer layer with a thickness of 100 μm and a radiation-resistant particle layer with a thickness of 10 μm disposed on the radiation-resistant polymer layer;

[0036] The radiation-resistant polymer layer comprises the following components in parts by weight: 100 parts silicone rubber and 8 parts nano AZO powder;

[0037] The components of the radiation-resistant particle layer include radiation-resistant glass particles and SEBS solution;

[0038] Radiation-resistant glass particles are composed of the following components by mass percentage: B2O3 3%, Li2O 7%, CeO2 2%, WO3 3%, MoO3 2%, Bi2O3 3.3%, with the balance being SiO2;

[0039] The preparation method of radiation-resistant glass particles includes the following steps:

[0040] A1. Weigh the raw materials according to the composition of the radiation-resistant glass particles, then melt and mix them. Add SnO2 and Sb2O3 in a mass ratio of 1:1 for clarification, followed by water quenching to obtain crude radiation-resistant glass particles; wherein the combined mass of SnO2 and Sb2O3 accounts for 1% of the mass of the raw materials.

[0041] A2. High-pressure physical pulverization method: The coarse anti-radiation glass particles are placed in a sealed container, pressurized to 8MPa and then depressurized to 0.13MPa for pulverization to obtain anti-radiation glass particles with a particle size of 25μm.

[0042] The preparation method of flexible radiation-resistant materials includes the following steps:

[0043] S1. Mix the radiation-resistant glass particles and the SEBS solution to obtain a mixture;

[0044] S2. The components of the radiation-resistant polymer layer are coated on the surface of the target substrate at 180°C and cured for 120 seconds to obtain the radiation-resistant polymer layer.

[0045] S3. Coat the mixture on the upper surface of the radiation-resistant polymer layer at 150°C and cure for 240 seconds to obtain a flexible radiation-resistant material.

[0046] Example 2

[0047] The flexible radiation-resistant material includes an 80 μm thick radiation-resistant polymer layer and a 15 μm thick radiation-resistant particle layer disposed on the radiation-resistant polymer layer.

[0048] The radiation-resistant polymer layer comprises the following components in parts by weight: 100 parts silicone rubber and 10 parts nano AZO powder;

[0049] The components of the radiation-resistant particle layer include radiation-resistant glass particles and SEBS solution;

[0050] Radiation-resistant glass particles are composed of the following components by mass percentage: 35% B2O, 5% Li2O, 4% CeO, 32% WO, 1.3% MoO, 32% Bi2O, with the balance being SiO2.

[0051] The preparation method of radiation-resistant glass particles includes the following steps:

[0052] A1. After weighing the raw materials according to the composition of the radiation-resistant glass particles, they are melt-mixed, and SnO2 and Sb2O3 in a mass ratio of 2:1 are added for clarification. The mixture is then water-quenched to obtain crude radiation-resistant glass particles; wherein the combined mass of SnO2 and Sb2O3 accounts for 1.5% of the mass of the raw materials.

[0053] A2. High-pressure physical pulverization method: Place the coarse anti-radiation glass particles in a sealed container, pressurize to 10MPa and then reduce the pressure to 0.08MPa for pulverization to obtain anti-radiation glass particles with a particle size of 20μm.

[0054] The preparation method of flexible radiation-resistant materials includes the following steps:

[0055] S1. Mix the radiation-resistant glass particles and the SEBS solution to obtain a mixture;

[0056] S2. The components of the radiation-resistant polymer layer are coated on the surface of the target substrate at 130°C and cured for 800 seconds to obtain the radiation-resistant polymer layer.

[0057] S3. Coat the mixture on the upper surface of the radiation-resistant polymer layer at 150°C and cure for 240 seconds to obtain a flexible radiation-resistant material.

[0058] Example 3

[0059] The flexible radiation-resistant material includes a radiation-resistant polymer layer with a thickness of 50 μm and a radiation-resistant particle layer with a thickness of 25 μm disposed on the radiation-resistant polymer layer.

[0060] The radiation-resistant polymer layer comprises the following components in parts by weight: 100 parts silicone rubber and 15 parts nano AZO powder;

[0061] The components of the radiation-resistant particle layer include radiation-resistant glass particles and SEBS solution;

[0062] Radiation-resistant glass particles are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 7%, WO3 1%, MoO3 1%, Bi2O3 1.6%, with the balance being SiO2.

[0063] The preparation method of radiation-resistant glass particles includes the following steps:

[0064] A1. After weighing the raw materials according to the composition of the radiation-resistant glass particles, they are melt-mixed, and SnO2 and Sb2O3 in a mass ratio of 1:2 are added for clarification. The mixture is then water-quenched to obtain crude radiation-resistant glass particles; wherein, the combined mass of SnO2 and Sb2O3 accounts for 2.5% of the mass of the raw materials.

[0065] A2. High-pressure physical pulverization method: Place the coarse anti-radiation glass particles in a sealed container, pressurize to 12MPa and then reduce the pressure to 0.13MPa for pulverization to obtain anti-radiation glass particles with a particle size of 10μm.

[0066] The preparation method of flexible radiation-resistant materials includes the following steps:

[0067] S1. Mix the radiation-resistant glass particles and the SEBS solution to obtain a mixture;

[0068] S2. The components of the radiation-resistant polymer layer are coated on the surface of the target substrate at 150°C and cured for 900 seconds to obtain the radiation-resistant polymer layer.

[0069] S3. Coat the upper surface of the radiation-resistant polymer layer with the mixture at 190°C and cure for 60 seconds to obtain a flexible radiation-resistant material.

[0070] Example 4

[0071] The only difference between this embodiment and Embodiment 3 is that the anti-radiation glass particles are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 7%, WO3 1%, MoO3 1%, Bi2O3 1.6%, Er2O3 1%, with the balance being SiO2.

[0072] Example 5

[0073] The only difference between this embodiment and Embodiment 3 is that the anti-radiation glass particles are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 7%, WO3 1%, MoO3 1%, Bi2O3 1.6%, Ta2O5 1%, with the balance being SiO2.

[0074] Example 6

[0075] The only difference between this embodiment and Embodiment 3 is that the anti-radiation glass particles are composed of the following components by mass percentage: B2O3 3%, Li2O 2.5%, CeO2 7%, WO3 1%, MoO3 1%, Bi2O3 1.6%, Er2O3 1%, Ta2O5 1%, with the balance being SiO2.

[0076] Example 7

[0077] The only difference between this embodiment and Embodiment 3 is that the radiation-resistant glass particles are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 7%, WO3 1%, MoO3 1%, Bi2O3 1.6%, Er2O3 3%, Ta2O5 1.5%, with the balance being SiO2.

[0078] Example 8

[0079] The only difference between this embodiment and Embodiment 3 is that the radiation-resistant glass particles are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 3%, WO3 1%, MoO3 1%, Bi2O3 1.6%, Er2O3 1.5%, Ta2O5 1.5%, with the balance being SiO2; wherein, CeO2+Er2O3+Ta2O5=6%.

[0080] Example 9

[0081] The difference between this embodiment and Embodiment 3 lies only in the radiation-resistant glass particles, which are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 6%, WO3 1%, MoO3 1%, Bi2O3 1.6%, Er2O3 3%, Ta2O5 1%, with the balance being SiO2; wherein, CeO2+Er2O3+Ta2O5=10%.

[0082] Example 10

[0083] The difference between this embodiment and Embodiment 3 lies only in the radiation-resistant glass particles, which are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 5%, WO3 1%, MoO3 1%, Bi2O3 1.6%, Er2O3 1%, Ta2O5 1.5%, with the balance being SiO2; wherein, CeO2+Er2O3+Ta2O5=7.5%.

[0084] Example 11

[0085] The difference between this embodiment and Embodiment 3 lies only in the radiation-resistant glass particles, which are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 5%, WO3 1%, MoO3 1%, Bi2O3 1.6%, Er2O3 2.5%, Ta2O5 1.2%, with the balance being SiO2; wherein, CeO2+Er2O3+Ta2O5=8.7%.

[0086] Comparative Example 1

[0087] Flexible radiation-resistant material, containing only a radiation-resistant polymer layer;

[0088] The radiation-resistant polymer layer comprises the following components in parts by weight: 100 parts silicone rubber and 15 parts nano AZO powder;

[0089] The preparation method of flexible radiation-resistant materials includes the following steps:

[0090] The components of the radiation-resistant polymer layer were coated onto the surface of the target substrate at 150°C and cured for 900 seconds to obtain a flexible radiation-resistant material.

[0091] Comparative Example 2

[0092] Flexible radiation-resistant material, containing only a radiation-resistant particle layer;

[0093] The components of the radiation-resistant particle layer include radiation-resistant glass particles and SEBS solution;

[0094] Radiation-resistant glass particles are composed of the following components by mass percentage: B2O3 8%, Li2O 2.5%, CeO2 7%, WO3 1%, MoO3 1%, Bi2O3 1.6%, with the balance being SiO2.

[0095] The preparation method of radiation-resistant glass particles includes the following steps:

[0096] A1. After weighing the raw materials according to the composition of the radiation-resistant glass particles, they are melt-mixed, and SnO2 and Sb2O3 in a mass ratio of 1:2 are added for clarification. The mixture is then water-quenched to obtain crude radiation-resistant glass particles; wherein, the combined mass of SnO2 and Sb2O3 accounts for 2.5% of the mass of the raw materials.

[0097] A2. High-pressure physical pulverization method: Place the coarse anti-radiation glass particles in a sealed container, pressurize to 12MPa and then reduce the pressure to 0.13MPa for pulverization to obtain anti-radiation glass particles with a particle size of 10μm.

[0098] The preparation method of flexible radiation-resistant materials includes the following steps:

[0099] After mixing radiation-resistant glass particles and SEBS solution, the mixture is coated onto the upper surface of the target substrate at 190°C and cured for 60 seconds to obtain a flexible radiation-resistant material.

[0100] Comparative Example 3

[0101] The only difference between this comparative example and Example 3 is that the radiation-resistant polymer layer includes only the following components by weight: 100 parts of silicone rubber;

[0102] The performance of the flexible radiation-resistant materials prepared in Examples 1-11 and Comparative Examples 1-3 were tested respectively.

[0103] According to standard ISO 9050:2003(E), the spectral transmittance of the sample before and after irradiation in the 330nm, 400nm, 450nm, and 500~2000nm bands was tested, and the relative attenuation values ​​at 400nm, 450nm, and 500~2000nm were calculated.

[0104] The spectral transmittance in the 500~2000nm band is taken as the average value;

[0105] Relative attenuation value = [(spectral transmittance before irradiation - spectral transmittance after irradiation) / spectral transmittance before irradiation] × 100%;

[0106] The test results are shown in Table 1.

[0107] Table 1 Radiation resistance test results

[0108]

[0109] By comparing the data of Examples 1-11 and Comparative Examples 1-3, it was found that, compared with Comparative Examples 1-3, the flexible radiation-resistant materials prepared in Examples 1-11 had lower spectral transmittance at 330 nm, higher spectral transmittance before and after irradiation at 400 nm, 450 nm, and 500-2000 nm, and lower relative attenuation values ​​after irradiation. This indicates that the radiation-resistant material adopts a double-layer structure, and the radiation-resistant particle layer and the radiation-resistant polymer layer work together to significantly improve the radiation resistance and radiation resistance stability of the radiation-resistant material.

[0110] Comparing the data from Examples 3-7, it was found that, compared with Examples 3-5, the flexible radiation-resistant materials prepared in Examples 6-7 had lower spectral transmittance at 330 nm, higher spectral transmittance before and after irradiation at 400 nm, 450 nm, and 500-2000 nm, and lower relative attenuation values ​​after irradiation. This indicates that introducing Er2O3 and Ta2O5 into the radiation-resistant glass particle composition of the radiation-resistant particle layer, in synergy with CeO2, can further improve the radiation resistance and radiation stability of the radiation-resistant material.

[0111] Comparing the data from Examples 6-9, it was found that, compared with Examples 6-7, the flexible radiation-resistant materials prepared in Examples 8-9 had lower spectral transmittance at 330 nm, higher spectral transmittance before and after irradiation at 400 nm, 450 nm, and 500-2000 nm, and lower relative attenuation values ​​after irradiation. This indicates that by limiting the composition of the radiation-resistant glass particles to 6%≤CeO2+Er2O3+Ta2O5≤10%, the radiation resistance and radiation stability of the radiation-resistant materials can be further improved.

[0112] Comparing the data from Examples 8-11, it was found that, compared with Examples 8-9, the flexible radiation-resistant materials prepared in Examples 10-11 had lower spectral transmittance at 330 nm, higher spectral transmittance before and after irradiation at 400 nm, 450 nm, and 500-2000 nm, and lower relative attenuation values ​​after irradiation. This indicates that by limiting the composition of the radiation-resistant glass particles to 7.5%≤CeO2+Er2O3+Ta2O5≤8.7%, the radiation resistance and radiation stability of the radiation-resistant materials can be further improved.

[0113] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A flexible radiation-resistant material, characterized in that, It includes a radiation-resistant polymer layer and a radiation-resistant particle layer disposed on the radiation-resistant polymer layer; The components of the radiation-resistant particle layer include radiation-resistant glass particles and a binder; The components of the radiation-resistant polymer layer include silicone rubber and nano-AZO powder; The radiation-resistant glass particles are composed of the following components by mass percentage: SiO2 70%~83%, B2O3 3%~8%, Li2O2 5%~7%, CeO2 2%~7%, WO3 1%~3%, MoO3 1%~2%, Bi2O3 1.6%~3.3%, Er2O3 1%~3%, Ta2O5 1%~1.5%, and 6%≤CeO2+Er2O3+Ta2O5≤10%.

2. The flexible radiation-resistant material according to claim 1, characterized in that, The radiation-resistant glass particles are composed of the following components by mass percentage: SiO2 70%~83%, B2O3 3%~8%, Li2O 2.5%~7%, CeO2 2%~7%, WO3 1%~3%, MoO3 1%~2%, Bi2O3 1.6%~3.3%, Er2O3 1%~3%, and Ta2O5 1%~1.5%, with 7.5%≤CeO2+Er2O3+Ta2O5≤8.7%.

3. The flexible radiation-resistant material according to claim 1, characterized in that, The method for preparing the radiation-resistant glass particles includes the following steps: A1. Weigh the raw materials according to the composition of the radiation-resistant glass particles, then melt and mix them, and quench them in water to obtain crude radiation-resistant glass particles. A2. The crude anti-radiation glass particles are post-processed to obtain anti-radiation glass particles with a particle size of 10~25μm.

4. The flexible radiation-resistant material according to claim 3, characterized in that, The post-processing involves first pressurizing to 8-12 MPa and then depressurizing to 0.08-0.13 MPa for pulverization.

5. The flexible radiation-resistant material according to claim 3, characterized in that, In step A1, a clarifying agent is added after the melt mixing for clarification treatment; the clarifying agent consists of SnO2 and Sb2O3; the mass of the clarifying agent accounts for 1% to 2.5% of the mass of the raw materials.

6. The flexible radiation-resistant material according to claim 1, characterized in that, The thickness of the radiation-resistant polymer layer is 50~100μm; the thickness of the radiation-resistant particle layer is 10~25μm.

7. A method for preparing a flexible radiation-resistant material according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1. Mix the radiation-resistant glass particles and the binder to obtain a mixture; S2. The components of the radiation-resistant polymer layer are coated onto the surface of the target substrate to obtain the radiation-resistant polymer layer; S3. Coat the mixture onto the upper surface of the radiation-resistant polymer layer to obtain a flexible radiation-resistant material.

8. The application of the flexible radiation-resistant material according to any one of claims 1 to 6 or the flexible radiation-resistant material prepared by the preparation method according to claim 7 in the protection of space batteries.

Images