A gamma-ray and neutron radiation shielding rubber material based on rare earth materials

Abstract

The present invention relates to the field of rubber, and specifically to a gamma-ray and neutron radiation protection rubber material based on rare earth materials. In the present invention, gadolinium hydride has a shielding effect on neutrons and γ-rays, while boron carbide also has an absorption effect on neutrons. In order to improve the dispersibility of boron carbide, the present invention first uses polydopamine to wrap nano boron carbide to prepare microcapsules, and then modifies the microcapsules with γ-aminopropyltriethoxysilane to make their surfaces rich in amino groups; after blending with graphene oxide, the amino groups will act on the oxygen-containing groups on the surface of graphene oxide and be successfully grafted onto the surface of graphene oxide. Relying on the network structure of graphene oxide, boron carbide can be well dispersed, and at the same time, the dispersibility of graphene oxide is also improved. After being modified by boron carbide and graphene oxide, the mechanical strength of the rubber material is improved, and it can be used to prepare glove box protective gloves and protective clothing, pipeline shielding, and key equipment shielding materials.

Description

Technical Field

[0001] The present invention relates to the technical field, and specifically to a gamma-ray and neutron radiation protection rubber material based on rare earth materials. Background Technique

[0002] Spent fuel, also known as irradiated nuclear fuel, is nuclear fuel that has been irradiated and used, usually produced by the nuclear reactor of a nuclear power plant. The nuclear fuel undergoes nuclear reactions after being bombarded by neutrons in the reactor and is unloaded from the reactor after a certain period of time. Since spent fuel contains a large number of elements or radionuclides that do not exist in nature and can only be obtained through nuclear reactions, these elements or radionuclides have extremely high scientific value, industrial value, and military value. Currently, in order to separate and extract these high-value elements from spent fuel, it is necessary to rely on operators to perform separation and purification operations in small amounts and multiple times. To protect the operators, gloves made of a rubber flexible material with neutron and γ-ray protection are required. By cooperating the gloves with a glove operation box with a protective effect, the radiation damage to the operators can be reduced to the minimum.

[0003] Currently, the technologies for preparing radiation-resistant rubber materials mainly have two major types: the static plastic method and the molding method. The shielding material with a three-layer structure manufactured by the static plastic method has the main drawback that delamination will occur between layers after irradiation tests; at the same time, the manufacturing equipment of this method is complex, the process is costly, and the cost is cumbersome. The single-layer lead-containing and tungsten-containing materials manufactured by the molding method only have a γ-ray protection effect and a poor neutron protection effect. Therefore, it is very necessary to invent a gamma-ray and neutron radiation protection rubber material based on rare earth materials. Summary of the Invention

[0004] The purpose of the present invention is to provide a gamma-ray and neutron radiation protection rubber material based on rare earth materials to solve the problems raised in the above background technique.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A gamma-ray and neutron radiation protection rubber material based on rare earth materials, and its preparation method includes the following steps:

[0006] Step 1: Mix a tris(hydroxymethyl)aminomethane buffer solution and absolute ethanol, add nano boron carbide powder, stir for 10 - 15 min, add dopamine hydrochloride, and stir at 25 - 35 °C for 5 - 8 h to obtain a mixed liquid;

[0007] Step 2: Add γ-aminopropyltriethoxysilane to the mixed liquid obtained in Step 1, raise the temperature to 50 - 60 °C, stir and react for 4 - 6 h. After centrifugation, filtration, washing, and drying, mix it with graphene oxide and add it to an ethanol solution, stir for 12 h, filter by suction, and dry to obtain a composite material;

[0008] Step 3: Plasticate the ethylene propylene diene monomer (EPDM). After the EPDM becomes sufficiently soft, mix it with rare earth material gadolinium hydride, rare earth dispersant, antioxidant, and composite material by internal mixing. After all the materials are sufficiently dispersed, take it out and let it stand for 24 - 30 h to obtain the raw rubber compound.

[0009] Step 4: Blend the raw rubber compound with sulfur and accelerator, make triangular bales 3 - 4 times, and then roll out the sheet. The product is obtained after two-stage vulcanization.

[0010] Furthermore, in Step 1, in the mixed liquid, the content of each component is by weight, 150 - 200 parts of tris(hydroxymethyl)aminomethane buffer solution, 50 - 60 parts of absolute ethanol, 2 - 5 parts of nano boron carbide powder, and 4 - 5 parts of dopamine hydrochloride.

[0011] Furthermore, in Step 1, the concentration of the tris(hydroxymethyl)aminomethane buffer solution is 1.2 - 1.8 g / L.

[0012] Furthermore, in Step 2, the dosage of each component is by weight, 100 - 120 parts of the mixed liquid A described in Step 1; 10 - 15 parts of γ-aminopropyltriethoxysilane; 15 - 20 parts of graphene oxide.

[0013] Furthermore, in Step 3, in the raw rubber compound, the content of each component is by weight percentage, 45 - 50% EPDM, 25 - 30% gadolinium hydride, 1 - 2% rare earth dispersant, 1 - 3% antioxidant, and 15 - 25% composite material.

[0014] Furthermore, in Step 3, the plasticating temperature is 80 - 90 °C and the plasticating time is 2 - 3 min; the internal mixing temperature is 100 - 120 °C and the internal mixing time is 8 - 10 min.

[0015] Furthermore, in Step 3, the rare earth dispersant is any one or two of titanate coupling agent and borate coupling agent; the antioxidant is any one or two of antioxidant RD and antioxidant 4010NA.

[0016] Furthermore, in Step 4, the content of each component is by weight, 100 - 110 parts of raw rubber compound, 1 - 5 parts of sulfur, and 1 - 5 parts of vulcanization accelerator.

[0017] Furthermore, in Step 4, the vulcanization accelerator is any one of 2-mercaptobenzothiazole, tetrasulfide bis(pentamethylene thiuram), dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazolyl sulfenamide, and tetramethylthiuram disulfide.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The flexible shielding material prepared by blending gadolinium hydride, nano-boron carbide and ethylene propylene diene monomer rubber has a stable internal structure, a high filler dispersion degree and good protection effect. As a rare earth material, gadolinium hydride can simultaneously achieve the shielding of neutrons and γ-rays, and its dispersibility in rubber can be effectively improved when used in combination with a rare earth dispersant; boron carbide has an absorption effect on neutrons and can play an auxiliary role, jointly improving the shielding effect with gadolinium hydride.

[0019] In order to further improve the dispersion effect of boron carbide in rubber, the present invention first uses polydopamine to wrap nano-boron carbide to prepare microcapsules, and then modifies the microcapsules with γ-aminopropyltriethoxysilane, so that the surface of the microcapsules is rich in amino groups. After being blended with graphene oxide, the surface amino groups will interact with the oxygen-containing groups on the surface of graphene oxide, and thus are successfully grafted onto the surface of graphene oxide. Relying on the network structure of graphene oxide, boron carbide can be well dispersed, and at the same time, the dispersibility of graphene oxide is also effectively improved. After being modified by boron carbide and graphene oxide, the mechanical strength of the rubber material is improved, and it can be used to prepare glove box protective gloves and protective clothing, pipeline shielding, and key equipment shielding materials. Specific embodiments

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0021] The raw materials and their sources used in the following examples are as follows:

[0022] Tris(hydroxymethyl)aminomethane (CAS No.: 77-86-1), ethanol (CAS No.: 64-17-5), dopamine hydrochloride (CAS No.: 62-31-7), γ-aminopropyltriethoxysilane (CAS No.: 919-30-2) are from Aladdin; graphene oxide is from Xianfeng Nano; nano-boron carbide is from Beijing Jia'anheng Technology; antioxidant 4010NA is from Shanghai Chengjin Chemical Industry; gadolinium hydride (CAS No.: 13572-97-9) is from Jiangxi Zhongxi Metal Materials Co., Ltd., model 3N, 200 mesh; rare earth dispersant is from Yangzhou Lida Resin Co., Ltd., which is a mixture of titanate coupling agent (model LD-A) and borate coupling agent (LD-100P) in a weight ratio of 1:1; ethylene propylene diene monomer rubber is from Dongguan Shenghao Plastics, product number: SH-5WEPDM, molecular weight 50000; sulfur (CAS No.: 7704-34-9) is from Hubei Xinrunde Chemical Industry; mercaptobenzothiazole (CAS No.: 155-04-4) is from Hubei Wande Chemical Industry.

[0023] Example 1:

[0024] Step 1: Mix 150 g of tris(hydroxymethyl)aminomethane buffer solution with a concentration of 1.2 g / L and 50 g of absolute ethanol, add 2 g of nano boron carbide powder, stir for 10 min, add 4 g of dopamine hydrochloride, and stir at 25 °C for 5 h. Then, centrifuge and filter to obtain a mixed liquid;

[0025] Step 2: Add 10 g of γ-aminopropyltriethoxysilane to 100 g of the mixed liquid obtained in Step 1, heat up to 50 °C, stir and react for 4 h. After centrifuging, filtering, washing, and drying, mix it with 15 g of graphene oxide and add it to 500 g of ethanol solution, stir for 12 h, filter by suction, and dry to obtain a composite material;

[0026] Step 3: Plasticate ethylene propylene diene monomer (EPDM) at 80 °C for 2 min. After the EPDM is fully softened, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and the composite material into a kneader, knead for 8 min, take it out after all materials are fully dispersed, and let it stand for 24 h to obtain raw rubber compound; Among them, the content of each component, by weight percentage, is 45% EPDM, 30% gadolinium hydride, 2% rare earth dispersant, 3% antioxidant 4010NA, and 20% composite material;

[0027] Step 4: Blend 100 kg of the raw rubber compound with 1 kg of sulfur and 1.5 kg of 2-mercaptobenzothiazole, make triangular bales 3 times, and then sheet out; Place it in a molding press, conduct the first vulcanization at 120 °C and 12 MPa, with a vulcanization time of 15 min; Then conduct the second vulcanization at 210 °C, with a vulcanization time of 5 h, to obtain the product.

[0028] Example 2:

[0029] Step 1: Mix 160 g of tris(hydroxymethyl)aminomethane buffer solution with a concentration of 1.3 g / L and 52 g of absolute ethanol, add 2.5 g of nano boron carbide powder, stir for 12 min, add 4.2 g of dopamine hydrochloride, and stir at 30 °C for 6 h to obtain a mixed liquid;

[0030] Step 2: Add 12 g of γ-aminopropyltriethoxysilane to 105 g of the mixed liquid obtained in Step 1, heat up to 55 °C, stir and react for 4.5 h. After centrifuging, filtering, washing, and drying, mix it with 16 g of graphene oxide and add it to 530 g of ethanol solution, stir for 12 h, filter by suction, and dry to obtain a composite material;

[0031] Step 3: Plasticate ethylene propylene diene monomer (EPDM) at 85 °C for 2.5 min. After the EPDM becomes sufficiently soft, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and composite material into a kneader, and knead for 8.5 min. After all the materials are sufficiently dispersed, take them out and let them stand for 26 h to obtain raw rubber compound; among them, the content of each component, by weight percentage, is 48% EPDM, 25% gadolinium hydride, 2% rare earth dispersant, 3% antioxidant 4010NA, and 22% composite material;

[0032] Step 4: Blend 103 kg of raw rubber compound with 2 kg of sulfur and 2.4 kg of 2-mercaptobenzothiazole, make four triangle packages, and then sheet out; Place it in a molding press and conduct the first vulcanization at 130 °C and 11 MPa for 20 min; Then conduct the second vulcanization at 215 °C for 3.5 h to obtain the product.

[0033] Example 3:

[0034] Step 1: Mix 180 g of tris(hydroxymethyl)aminomethane buffer solution with a concentration of 1.4 g / L and 56 g of absolute ethanol, add 4 g of nano boron carbide powder, stir for 13 min, add 4.4 g of dopamine hydrochloride, and stir at 35 °C for 7 h to obtain a mixed liquid;

[0035] Step 2: Add 14 g of γ-aminopropyltriethoxysilane to 118 g of the mixed liquid described in Step 1, raise the temperature to 55 °C, stir and react for 5 h. After centrifugation, filtration, washing, and drying, mix it with 17 g of graphene oxide and add it to 580 g of ethanol solution, stir for 12 h, filter with suction, and dry to obtain a composite material;

[0036] Step 3: Plasticate EPDM at 87 °C for 2 min. After the EPDM becomes sufficiently soft, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and composite material into a kneader, and knead for 10 min. After all the materials are sufficiently dispersed, take them out and let them stand for 25 h to obtain raw rubber compound; among them, the content of each component, by weight percentage, is 47% EPDM, 25% gadolinium hydride, 2% rare earth dispersant, 1% antioxidant 4010NA, and 25% composite material;

[0037] Step 4: Blend 102 kg of raw rubber compound with 3 kg of sulfur and 2 kg of 2-mercaptobenzothiazole, make four triangle packages, and then sheet out; Place it in a molding press and conduct the first vulcanization at 145 °C and 10 MPa for 18 min; Then conduct the second vulcanization at 220 °C for 4 h to obtain the product.

[0038] Example 4:

[0039] Step 1: Mix 190 g of tris(hydroxymethyl)aminomethane buffer solution with a concentration of 1.5 g / L and 53 g of absolute ethanol, add 4 g of nano boron carbide powder, stir for 12 min, add 4.6 g of dopamine hydrochloride, and stir at 30 °C for 6 h to obtain a mixed liquid;

[0040] Step 2: Add 12 g of γ-aminopropyltriethoxysilane to 114 g of the mixed liquid obtained in Step 1, raise the temperature to 53 °C, stir and react for 5.5 h. After centrifugation, filtration, washing, and drying, mix it with 18 g of graphene oxide and add it to 550 g of ethanol solution, stir for 12 h, filter by suction, and dry to obtain a composite material;

[0041] Step 3: Plasticate ethylene propylene diene monomer (EPDM) at 85 °C for 2.5 min. After the EPDM is fully softened, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and the composite material into a kneader, knead for 8 min, take it out after the materials are fully dispersed, and let it stand for 27 h to obtain raw rubber compound; Among them, the content of each component, by weight percentage, is 46% EPDM, 30% gadolinium hydride, 2% rare earth dispersant, 2% antioxidant 4010NA, and 20% composite material;

[0042] Step 4: Blend 108 kg of raw rubber compound with 4.3 kg of sulfur and 3.8 kg of 2-mercaptobenzothiazole, make a triangular package 4 times, and then sheet out; Place it in a molding press, carry out the first vulcanization at 160 °C and 11 MPa, with a vulcanization time of 22 min; Then carry out the second vulcanization at 210 °C, with a vulcanization time of 4.5 h to obtain the product.

[0043] Example 5:

[0044] Step 1: Mix 175 g of tris(hydroxymethyl)aminomethane buffer solution with a concentration of 1.6 g / L and 51 g of absolute ethanol, add 3 g of nano boron carbide powder, stir for 12 min, add 4.8 g of dopamine hydrochloride, and stir at 33 °C for 7 h to obtain a mixed liquid;

[0045] Step 2: Add 13 g of γ-aminopropyltriethoxysilane to 117 g of the mixed liquid obtained in Step 1, raise the temperature to 52 °C, stir and react for 5 h. After centrifugation, filtration, washing, and drying, mix it with 17 g of graphene oxide and add it to 575 g of ethanol solution, stir for 12 h, filter by suction, and dry to obtain a composite material;

[0046] Step 3: Plasticate ethylene propylene diene monomer (EPDM) at 85 °C for 2 min. After the EPDM becomes fully soft, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and composite material into a mixer and knead for 9 min. After all materials are fully dispersed, take out and let stand for 28 h to obtain raw rubber compound; among them, the content of each component, by weight percentage, is 49% EPDM, 28% gadolinium hydride, 2% rare earth dispersant, 1% antioxidant 4010NA, and 20% composite material;

[0047] Step 4: Blend 109 kg of raw rubber compound with 4 kg of sulfur and 4.7 kg of 2-mercaptobenzothiazole, make triangular packages 3 - 4 times, and then sheet out; place it in a mold press and conduct the first vulcanization at 165 °C and 11 MPa for 23 min; then conduct the second vulcanization at 215 °C for 4.5 h to obtain the product.

[0048] Example 6:

[0049] Step 1: Mix 200 g of tris(hydroxymethyl)aminomethane buffer solution with a concentration of 1.2 - 1.7 g / L and 60 g of absolute ethanol, add 5 g of nano boron carbide powder, stir for 10 min, add 5 g of dopamine hydrochloride, and stir at 35 °C for 8 h to obtain a mixed liquid;

[0050] Step 2: Add 15 g of γ-aminopropyltriethoxysilane to 120 g of the mixed liquid obtained in Step 1, raise the temperature to 60 °C, stir and react for 6 h. After centrifugation, filtration, washing, and drying, mix it with 20 g of graphene oxide and add it to 600 g of ethanol solution, stir for 12 h, filter by suction, and dry to obtain a composite material;

[0051] Step 3: Plasticate EPDM at 90 °C for 3 min. After the EPDM becomes fully soft, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and composite material into a mixer and knead for 10 min. After all materials are fully dispersed, take out and let stand for 30 h to obtain raw rubber compound; among them, the content of each component, by weight percentage, is 50% EPDM, 30% gadolinium hydride, 2% rare earth dispersant, 3% antioxidant 4010NA, and 15% composite material;

[0052] Step 4: Blend 110 kg of raw rubber compound with 5 kg of sulfur and 5 kg of 2-mercaptobenzothiazole, make triangular packages 4 times, and then sheet out; place it in a mold press and conduct the first vulcanization at 170 °C and 12 MPa for 25 min; then conduct the second vulcanization at 220 °C for 5 h to obtain the product.

[0053] Comparative Example 1:

[0054] Prepare rubber without adding composite material.

[0055] Step 1: Plasticate ethylene propylene diene monomer (EPDM) at 80 °C for 2 min. After the EPDM becomes fully soft, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and composite material into an internal mixer, and carry out internal mixing for 8 min. After all materials are fully dispersed, take out and let stand for 24 h to obtain raw rubber compound; among them, the content of each component, by weight percentage, is 45% EPDM, 30% gadolinium hydride, 2% rare earth dispersant, 3% antioxidant 4010NA, and 20% composite material;

[0056] Step 2: Blend 100 kg of the raw rubber compound with 1 kg of sulfur and 1.5 kg of 2-mercaptobenzothiazole, make triangular packages 3 times, and then sheet out; place it in a molding press, and carry out the first vulcanization at 120 °C and 12 MPa for 15 min; then carry out the second vulcanization at 210 °C for 5 h to obtain the product.

[0057] Comparative Example 2:

[0058] Prepare rubber without adding gadolinium hydride.

[0059] Step 1: Mix 160 g of a tris(hydroxymethyl)aminomethane buffer solution with a concentration of 1.3 g / L and 52 g of absolute ethanol, add 2.5 g of nano boron carbide powder, stir for 12 min, add 4.2 g of dopamine hydrochloride, and stir at 30 °C for 6 h to obtain a mixed liquid;

[0060] Step 2: Add 12 g of γ-aminopropyltriethoxysilane to 105 g of the mixed liquid A in Step 1, heat up to 55 °C, stir and react for 4.5 h. After centrifugation, filtration, washing, and drying, mix it with 16 g of graphene oxide and add it to 530 g of an ethanol solution, stir for 12 h, filter by suction and dry to obtain a composite material;

[0061] Step 3: Plasticate EPDM at 85 °C for 2.5 min. After the EPDM becomes fully soft, add rare earth material antioxidant 4010NA and composite material into an internal mixer, and carry out internal mixing for 8.5 min. After all materials are fully dispersed, take out and let stand for 26 h to obtain raw rubber compound; among them, the content of each component, by weight percentage, is 75% EPDM, 3% antioxidant 4010NA, and 22% composite material;

[0062] Step 4: Blend 103 kg of the raw rubber compound with 2 kg of sulfur and 2.4 kg of 2-mercaptobenzothiazole, make triangular packages 4 times, and then sheet out; place it in a molding press, and carry out the first vulcanization at 130 °C and 11 MPa for 20 min; then carry out the second vulcanization at 215 °C for 3.5 h to obtain the product.

[0063] Comparative Example 3:

[0064] Prepare the composite material without adding graphene oxide.

[0065] Step 1: Mix 180 g of tris(hydroxymethyl)aminomethane buffer solution with a concentration of 1.4 g / L and 56 g of absolute ethanol, add 4 g of nano boron carbide powder, stir for 13 min, add 4.4 g of hydrochloric acid dopamine, and stir at 35 °C for 7 h to obtain a mixed liquid. Centrifuge and filter to obtain the composite material.

[0066] Step 2: Plasticize ethylene propylene diene monomer (EPDM) at 87 °C for 2 min. After the EPDM is fully softened, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and the composite material into a mixer and knead for 10 min. Take it out after the materials are fully dispersed and let it stand for 25 h to obtain the raw rubber compound. Among them, the content of each component, by weight percentage, is 47% EPDM, 25% gadolinium hydride, 2% rare earth dispersant, 1% antioxidant 4010NA, and 25% polydopamine microcapsules.

[0067] Step 4: Blend 102 kg of the raw rubber compound with 3 kg of sulfur and 2 kg of 2-mercaptobenzothiazole, make a triangular package 4 times, and then sheet out; place it in a mold press and conduct the first vulcanization at 145 °C and 10 MPa for 18 min; then conduct the second vulcanization at 220 °C for 4 h to obtain the product.

[0068] Comparative Example 4:

[0069] Prepare the composite material by directly blending boron carbide and graphene oxide.

[0070] Step 1: Stir 4 g of nano boron carbide powder with 18 g of graphene oxide to obtain the composite material.

[0071] Step 2: Plasticize EPDM at 85 °C for 2.5 min. After the EPDM is fully softened, add rare earth material gadolinium hydride, rare earth dispersant, antioxidant 4010NA, and the composite material into a mixer and knead for 8 min. Take it out after the materials are fully dispersed and let it stand for 27 h to obtain the raw rubber compound. Among them, the content of each component, by weight percentage, is 46% EPDM, 30% gadolinium hydride, 2% rare earth dispersant, 2% antioxidant 4010NA, and 20% composite material.

[0072] Step 3: Blend 108 kg of the raw rubber compound with 4.3 kg of sulfur and 3.8 kg of 2-mercaptobenzothiazole, make a triangular package 4 times, and then sheet out; place it in a mold press and conduct the first vulcanization at 160 °C and 11 MPa for 22 min; then conduct the second vulcanization at 210 °C for 4.5 h to obtain the product.

[0073] Experiment:

[0074] Tensile properties: Using a HY-5080 universal tensile testing machine, according to the method specified in GB / T528-2009, the rubber was cut into dumbbell shapes (size: 4mm×75mm×2mm), and the tensile strength and elongation at break were tested at a tensile speed of 100mm / min;

[0075] Thermal neutron shielding test: Using a thermal neutron beam moderated by a 10Ci 241 Am-Be neutron source through 75cm of high-purity graphite for experiments. An experiment was conducted by fabricating a 2mm-thick cadmium collimator to wrap and collimate the detector, with a 30mm opening at the front end of the collimator; The He-3 proportional counter model sp90 was used as the thermal neutron detector to conduct tests at a total of 4 positions on the palm, wrist, forearm, and posterior arm of the sample;

[0076] γ-ray shielding: Using a γ-ray air kerma (shielding level) standard device, referring to the standard document GB / Z147-2002 for experiments, and using a 30cc ionization chamber to conduct tests at a total of 4 positions on the palm, wrist, forearm, and posterior arm of the sample to be tested.

[0077]

[0078]

[0079] Conclusion:

[0080] The data of Examples 1 to 6 show that the rubber material prepared by the present invention not only has good shielding effects on gamma rays and neutron radiation, but also has excellent physical properties. Taking Example 1 as a reference, the data of Comparative Example 1 show that the mechanical properties of the rubber prepared without adding the composite material are poor, indicating that graphene oxide and boron carbide have a toughening and modifying effect on the rubber; Taking Example 2 as a reference, the data of Comparative Example 2 show that the shielding effect of the rubber prepared without adding gadolinium hydride on gamma rays decreases significantly, and the shielding effect on thermal neutrons is 50%, mainly because boron carbide is present; Taking Examples 3 to 4 as references, the data of Comparative Examples 3 to 4 show that graphene oxide and polydopamine microcapsules improve the dispersibility by relying on the interaction between the two, and neither can be missing. In addition, after the rubber material prepared by the present invention is irradiated with 1000KGy, the tear strength is greater than 8Mpa and the elongation at break is greater than 400%; In terms of chemical resistance, the resistance to penetration of strong acids and strong alkalis is greater than level 6, and it can be used for the preparation of glove box protective gloves, protective clothing, pipeline shielding, and shielding materials for key equipment.

[0081] Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a gamma-ray and neutron radiation protection rubber material based on rare earth materials, characterized in that: Step 1: Mix tris(hydroxymethyl)aminomethane buffer solution and absolute ethanol, add nano boron carbide powder, stir for 10 - 15 min, add dopamine hydrochloride, and stir at 25 - 35 °C for 5 - 8 h to obtain a mixed liquid; Step 2: Add γ-aminopropyltriethoxysilane to the mixed liquid obtained in Step 1, raise the temperature to 50 - 60 °C, stir and react for 4 - 6 h. After centrifugation, filtration, washing, and drying, mix with graphene oxide and add it to an ethanol solution, stir for 12 h, filter by suction and dry to obtain a composite material; Step 3: Plasticize ethylene propylene diene monomer rubber. After the ethylene propylene diene monomer rubber is fully softened, mix and knead it with rare earth material gadolinium hydride, rare earth dispersant, antioxidant, and the composite material. After each material is fully dispersed, take it out and let it stand for 24 - 30 h to obtain raw rubber compound; Step 4: Blend the raw rubber compound with sulfur and vulcanization accelerator, make triangular packages 3 - 4 times, and then sheet out; After two-stage vulcanization, the product is obtained; In Step 1, in the mixed liquid, the content of each component is calculated by weight, 150 - 200 parts of tris(hydroxymethyl)aminomethane buffer solution, 50 - 60 parts of absolute ethanol, 2 - 5 parts of nano boron carbide powder, 4 - 5 parts of dopamine hydrochloride; In Step 2, the dosage of each component is calculated by weight, 100 - 120 parts of the mixed liquid described in Step 1; 10 - 15 parts of γ-aminopropyltriethoxysilane; 15 - 20 parts of graphene oxide; In Step 3, in the raw rubber compound, the content of each component is calculated by weight percentage, 45 - 50% ethylene propylene diene monomer rubber, 25 - 30% gadolinium hydride, 1 - 2% rare earth dispersant, 1 - 3% antioxidant, 15 - 25% composite material.

2. The preparation method of a gamma-ray and neutron radiation protection rubber material based on rare earth materials according to claim 1, characterized in that: In Step 3, the plasticizing temperature is 80 - 90 °C, and the plasticizing time is 2 - 3 min; The kneading temperature is 100 - 120 °C, and the kneading time is 8 - 10 min.

3. The preparation method of a gamma ray and neutron radiation protection rubber material based on rare earth materials according to claim 1, characterized in that: In Step 3, the rare earth dispersant is any one or two of titanate coupling agent and borate coupling agent; The antioxidant is any one or two of antioxidant RD and antioxidant 4010NA.

4. The preparation method of a gamma-ray and neutron radiation protection rubber material based on rare earth materials according to claim 1, characterized in that: In Step 4, the content of each component is calculated by weight, 100 - 110 parts of raw rubber compound, 1 - 5 parts of sulfur, 1 - 5 parts of vulcanization accelerator.

5. The preparation method of a gamma-ray and neutron radiation protection rubber material based on rare earth materials according to claim 1, characterized in that: In Step 4, the vulcanization accelerator is any one of 2-mercaptobenzothiazole, tetrasulfide bis(pentamethylene thiuram), dibenzothiazole disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram disulfide.

6. A protective rubber material prepared by the preparation method of a gamma-ray and neutron radiation protection rubber material based on rare earth materials according to any one of claims 1 - 5.

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