Rubber product with self-cleaning and radiation protection functions and preparation method thereof

Abstract

The invention belongs to the technical field of radiation protection and super-hydrophobic coatings, and particularly relates to a rubber product with self-cleaning and radiation protection functions and a preparation method thereof. The radiation source is gamma rays in a 241Am source and / or a 252Cf neutron source and / or a reactor thermal neutron source; the rubber product comprises an optional gamma ray shielding layer, an optional neutron shielding layer and a self-cleaning layer which are sequentially arranged from inside to outside; at least one gamma-ray shielding layer and at least one neutron shielding layer are arranged; the gamma-ray shielding layer and the neutron shielding layer are both of a multi-layer structure. The rubber product with the self-cleaning and radiation protection functions, provided by the invention, has the advantages of strong shielding target pertinence, excellent neutron and gamma ray comprehensive shielding effect, outstanding self-cleaning capability, good flexibility, strong mechanical stability, various application scenes and relatively high application value.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of radiation protection and super-hydrophobic coating, and particularly relates to a rubber product with self-cleaning and radiation protection functions and a preparation method thereof. BACKGROUND

[0002] With the deep integration of nuclear technology and nuclear power, medical treatment, industry and other fields and the improvement of people's nuclear safety awareness, rubber radiation protection products are needed to protect the operating personnel in nuclear-related places and the instruments and equipment with complex configurations. The rubber radiation protection products include protective gloves, protective clothing, protective headgear, equipment shielding covers, wall shielding layers and the like. In addition to good protection performance, such protection products are also light and flexible, comfortable to wear, easy to process and convenient to replace.

[0003] In addition, during the disposal of nuclear waste, neutrons and gamma rays are accompanied, the protection of neutrons often needs to consider secondary gamma rays, and the neutron source often produces gamma rays, which requires the protection products to have comprehensive protection functions of neutrons and gamma rays. In a high radiation environment, radioactive particles such as aerosols and dust will adhere to the surface of the protection products, and artificial wiping or high-pressure flushing decontamination is easy to produce aerosols, causing pollution migration, and the cost of waste water treatment is high. In addition, frequent replacement of high-cost protection products is economically poor and generates a large amount of radioactive waste. In addition, the protection products contaminated with radioactive particles have the risk of spreading to clean areas when moving or detaching, causing cross-contamination of the environment and increasing the safety risk of the protection personnel.

[0004] Therefore, in order to ensure the health of the operating personnel and the safety of the environment, a neutron and gamma ray protection product capable of removing surface radioactive particles by simple blowing or normal pressure flushing is needed. SUMMARY

[0005] In view of the above problems, one of the purposes of the present application is to provide a rubber product with self-cleaning and radiation protection functions and a preparation method thereof, which can realize efficient shielding of 241 gamma rays in Am source and / or 252 Cf neutron source and / or reactor thermal neutron source, and has a self-cleaning function for radioactive particles.

[0006] The second purpose of the present application is to provide a preparation method of the rubber product.

[0007] To this end, the first aspect of the present application provides a rubber product with self-cleaning and radiation protection functions, and the radiation source is: 241 gamma rays in Am source and / or 252The rubber product of the Cf neutron source and / or reactor thermal neutron source comprises: an optional gamma ray shielding layer, an optional neutron shielding layer, and a self-cleaning layer arranged in sequence from inside to outside; the gamma ray shielding layer and the neutron shielding layer are at least one; the gamma ray shielding layer and the neutron shielding layer are both multi-layer structures; The gamma ray shielding layer comprises a tin oxide layer, an erbium oxide layer, and a bismuth oxide layer arranged in sequence from inside to outside; The neutron shielding layer comprises a boron carbide layer, a boron nitride layer, a lithium chloride layer, and a gadolinium boride layer arranged in sequence from inside to outside; The layers inside the neutron shielding layer and the gamma ray shielding layer are formed by dispersing shielding fillers of tin oxide, erbium oxide, bismuth oxide, boron carbide, boron nitride, lithium chloride, or gadolinium boride in a shielding filler dispersion liquid, and then mixing the rubber latex and the compounding agent, and drying; The self-cleaning layer is formed by spraying or dipping a self-cleaning material.

[0008] The rubber product with self-cleaning and radiation protection functions of the present application, from inside to outside, "inside" refers to the protected side; "outside" refers to the direction of the radiation source (field).

[0009] The rubber product with self-cleaning and radiation protection functions of the present application, when only the gamma ray shielding layer is provided, indicates that the radiation source (field) is mainly gamma rays; when only the neutron shielding layer is provided, indicates that the radiation source (field) is mainly neutron rays.

[0010] As a preferred solution, the rubber product with self-cleaning and radiation protection functions described above, the rubber latex comprises one or more of natural latex, styrene-butadiene latex, carboxyl styrene-butadiene latex, polyurethane latex, chlorobutadiene latex, nitrile-butadiene latex, ethylene-propylene latex, butyl latex, and chlorosulfonated polyethylene latex.

[0011] As a preferred solution, the rubber product with self-cleaning and radiation protection functions described above, in a single layer of the gamma ray shielding layer, 100 parts by weight of rubber latex, 4-50 parts by weight of compounding agent, and 30-500 parts of gamma ray shielding filler, based on dry rubber.

[0012] As a preferred solution, the rubber product with self-cleaning and radiation protection functions described above, in a single layer of the neutron shielding layer, 100 parts by weight of rubber latex, 4-50 parts by weight of compounding agent, and 20-500 parts of neutron shielding filler, based on dry rubber.

[0013] As a preferred solution, the rubber product with self-cleaning and radiation protection functions described above, the compounding agent comprises one or more of 0.5-7 parts by weight of vulcanizing agent, 0.5-15 parts by weight of accelerator, 1-20 parts by weight of active agent, 0.1-5 parts by weight of antioxidant, 0.1-4 parts by weight of dispersant, 0.1-3 parts by weight of stabilizer, and 0.001-2 parts by weight of thickening agent.

[0014] As a further preferred solution, in the rubber product with self-cleaning and radiation protection functions mentioned above: The vulcanizing agent is sulfur and / or 4,4'-dithiodimorpholine; The accelerator is zinc diethyl dithiocarbamate and / or zinc ethyl phenyl dithiocarbamate; The active agent is zinc oxide and / or zinc carbonate; The antioxidant used is one or more of N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, N-isopropyl-N'-phenyl-p-phenylenediamine, and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine; The dispersing agent is sodium methylene dithiophenyl sulfonate and / or potassium pyrophosphate; The stabilizer is casein and / or potassium hydroxide; The thickening agent is one or more of sodium polyacrylate, ammonium polymethacrylate, methyl cellulose, sodium alginate, and hydroxyethyl cellulose.

[0015] As a preferred solution, in the rubber product with self-cleaning and radiation protection functions mentioned above, the particle size of the shielding filler tin oxide, erbium oxide, bismuth oxide, boron carbide, boron nitride, lithium chloride, or gadolinium boride ranges from 0.02 to 50 μm.

[0016] As a preferred solution, in the rubber product with self-cleaning and radiation protection functions mentioned above, the raw material mass composition of the self-cleaning layer includes 3%-20% polydimethylsiloxane, 1%-12% solid particles, 60.5%-92% organic solvent, 0.3%-6% crosslinking agent, and 0.1%-1.5% catalyst. The self-cleaning effect of super-hydrophobicity, anti-fouling, and anti-adhesion is achieved through the design of low surface energy substance (polydimethylsiloxane) + micro-nano rough structure, and the crosslinking system ensures the firm combination of the coating and the rubber shielding layer.

[0017] As a further preferred solution, in the rubber product with self-cleaning and radiation protection functions mentioned above: the solid particles include one or more of silicon dioxide, graphene, carbon nanotubes, and carbon black, and more preferably, in the solid particles, the mass ratio of solid particles with a particle size in the micron range and solid particles with a particle size in the nanometer range is 100:15-25. The micro-nano structure formed on the surface of the self-cleaning layer by the micron and nanometer solid particles enhances the self-cleaning ability of the coating.

[0018] As a further preferred solution, the organic solvent includes one or more of ethanol, isopropyl alcohol, acetone, n-hexane, cyclohexane, and tetrahydrofuran.

[0019] As a further preferred solution, the cross-linking agent comprises one or more of polybutadiene, tetraethyl orthosilicate, perfluoroalkylethyltrimethoxysilane, hexamethyldisilazane.

[0020] As a further preferred solution, the catalyst comprises one or more of tert-butyl peroxybenzoate, dibutyltin dilaurate, diazabicycloundecane, tetraisopropyl titanate.

[0021] As a preferred solution, in the rubber product with self-cleaning and radiation protection functions mentioned above: The thickness of the tin oxide layer is 0.4-1.2mm; The thickness of the erbium oxide layer is 0.6-1.5mm; The thickness of the bismuth oxide layer is 1-2.2mm; The thickness of the boron carbide layer is 0.5-8mm; The thickness of the boron nitride layer is 0.1-6mm; The thickness of the lithium chloride layer is 0.1-6mm; The thickness of the gadolinium boride layer is 0.1-1.5mm.

[0022] As a further preferred solution, in the rubber product with self-cleaning and radiation protection functions mentioned above: The thickness of the tin oxide layer is 0.6-0.7mm; The thickness of the erbium oxide layer is 0.8-0.9mm; The thickness of the bismuth oxide layer is 1.4-1.6mm; The thickness of the boron carbide layer is 0.8-6.5mm; The thickness of the boron nitride layer is 0.2-4.5mm; The thickness of the lithium chloride layer is 0.2-4.5mm; The thickness of the gadolinium boride layer is 0.15-1.1mm.

[0023] The arrangement has a higher protection efficiency for continuous energy spectrum gamma rays and neutron rays than a single material, and can effectively avoid the problems of over-hardness and poor flexibility of the product caused by the use of an excessively thick single high-density material, while achieving a predetermined shielding effect, and the multi-layer design is more lightweight under the premise of ensuring the protection effect. Under the premise of ensuring the protection effect, the waste of materials is avoided, the secondary gamma rays are reduced, and the lightweight design of the material is embodied.

[0024] The second aspect of the present application provides a preparation method of the rubber product with self-cleaning and radiation protection functions mentioned above, and the preparation method comprises: forming the gamma ray shielding layer and / or the neutron shielding layer on the mold in sequence by a dipping process; the gamma ray shielding layer: forming a tin oxide layer, an erbium oxide layer, and a bismuth oxide layer in sequence; The neutron shielding layer: sequentially forming a boron carbide layer, a boron nitride layer, a lithium chloride layer, and a gadolinium boride layer; Drying and demolding; Forming the self-cleaning layer by a spraying or dipping process; Drying to obtain the rubber product with self-cleaning and radiation protection functions.

[0025] As a preferred solution, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane can be dipped on the finished product and dried to further enhance the self-cleaning ability thereof.

[0026] According to the present application, in one specific embodiment, the suspension for preparing the self-cleaning layer is prepared by dissolving a crosslinking agent and a catalyst in an organic solvent, stirring and dissolving polydimethylsiloxane, and then adding solid particles and ultrasonicating to form a suspension. Preferably, the stirring time is 30-120 minutes; preferably, the ultrasonicating time is 30-120 minutes.

[0027] According to the present application, in one specific embodiment, the clean mold is immersed in a coagulant, dried and cooled to obtain the mold to be used. Preferably, the mold temperature is 20-150 ℃; preferably, the coagulant comprises one or more of a calcium chloride aqueous solution, a calcium nitrate aqueous solution, a zinc chloride aqueous solution, a zinc nitrate aqueous solution, a magnesium sulfate aqueous solution, and a magnesium chloride aqueous solution; preferably, the coagulant aqueous solution temperature is 45-100 ℃; preferably, the mold immersion time is 5-60 seconds; preferably, the mold drying temperature is 80-200 ℃.

[0028] According to the present application, in one specific embodiment, the single layer in the gamma ray shielding layer is prepared by immersing the mold in a rubber compound emulsion containing tin oxide, and then drying to shape the rubber dipping layer, and repeating the dipping process multiple times to make the prepared tin oxide layer reach the desired thickness. The erbium oxide layer and the bismuth oxide layer are also prepared according to the above method. Preferably, the rubber compound emulsion temperature is 20-70 ℃; preferably, the immersion time is 5-60 seconds; preferably, the mold lifting speed is 1 cm / min-30 cm / min; preferably, the drying temperature of the mold immersed in the single layer rubber compound emulsion of the gamma ray shielding layer is 45-125 ℃; preferably, the drying time is 1-60 minutes.

[0029] According to the present application, in one specific embodiment, the single layer in the neutron shielding layer is prepared by immersing the mold into the rubber compound emulsion containing boron carbide, then drying, shaping the rubber impregnated layer, repeating the impregnation process multiple times, and making the prepared boron carbide layer reach the desired thickness. The boron nitride layer, lithium chloride layer and gadolinium boride layer are also prepared according to the above method. Preferably, the temperature of the rubber compound emulsion is 20-70℃; preferably, the immersion time is 5-60 seconds; preferably, the mold pulling speed is 1-30 cm / min; preferably, the drying temperature of the mold immersed in the single layer rubber compound emulsion of the gamma ray shielding layer is 45-125℃; preferably, the drying time is 1-60 minutes.

[0030] According to the present application, in one specific embodiment, before preparing the self-cleaning layer, dry demolding: dry the semi-finished product at 50-120℃ for 30-120 minutes to fully shape the rubber product, then evenly apply a release agent and a release agent on the surface, after demolding, cook in hot water at 50-100℃ for 30-80 minutes, and after taking out, dry at 30-110℃ for 20-100 minutes. Preferably, the release agent or release agent is one or more of mica powder, talc powder, starch, calcium carbonate.

[0031] According to the present application, in one specific embodiment, the self-cleaning layer is prepared by immersing the suspension used for the self-cleaning layer for 1-20 minutes, then drying to obtain a rubber product with self-cleaning and radiation protection functions; or the suspension used for the self-cleaning layer is filled into a spray gun, and the spray gun is moved back and forth 2-15 times at a pressure of 0.2-0.8 MPa and a distance of 10-25 cm from the semi-finished product, then dried to obtain a rubber product with self-cleaning and radiation protection functions. Preferably, the drying temperature is 50-150℃; preferably, the drying time is 4-45 minutes.

[0032] Compared with the prior art, the present application at least includes the following beneficial effects: In the present application, the self-cleaning layer is compounded with the radiation shielding layer by immersion or spraying and curing, in addition to excellent self-cleaning ability, it also has good mechanical stability.

[0033] The rubber product with self-cleaning and radiation protection functions provided by the present application has the advantages of strong shielding target specificity, excellent comprehensive shielding effect of neutrons and gamma rays, outstanding self-cleaning ability, good flexibility, strong mechanical stability, diverse application scenarios, and high application value.

[0034] The above description is only a summary of the technical solutions of the present application, in order to more clearly understand the technical means of the present application, and to be able to implement according to the content of the specification, and in order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 A cross-sectional structure and a radiation shielding schematic diagram of a specific embodiment of the rubber product with self-cleaning and radiation protection functions. DETAILED DESCRIPTION

[0036] In the following description, a large number of specific details are given to provide a more thorough understanding of the technical solutions provided by the present application. However, it should be apparent to one of ordinary skill in the art that the technical solutions provided by the present application can be implemented without one or more of these details.

[0037] In the examples and comparative examples of the present application, the raw materials are derived from commercial products.

[0038] In a specific embodiment, the rubber product with self-cleaning and radiation protection functions provided by the present application comprises, from inside to outside, a gamma ray shielding layer, a neutron shielding layer, and a self-cleaning layer; the gamma ray shielding layer and the neutron shielding layer are both multi-layer structures, where "inside" refers to the protected side, and "outside" refers to the direction of the radiation source (field), see Figure 1 .

[0039] Example 1 (1) Preparation of the suspension for the self-cleaning layer In a fume hood, polybutadiene and tert-butyl peroxybenzoate were added to n-hexane while stirring, and stirring was continued for 40 minutes until both were dissolved; then polydimethylsiloxane was added, and stirring was continued for 60 minutes until complete dissolution, followed by the addition of hydrophobic silica particles (micron silica mass: nanometer silica mass = 100:20), and ultrasonic treatment was performed for 100 minutes to obtain the suspension for the self-cleaning layer (mass composition: 5% polydimethylsiloxane, 2% hydrophobic silica solid particles, 1% polybutadiene crosslinking agent, 0.3% catalyst, and the balance n-hexane).

[0040] (2) Preparation of the gamma ray shielding single-layer rubber compound emulsion (2.1) Ball milling of the shielding filler: the corresponding gamma ray shielding filler was ball milled according to the following composition: 225 parts of bismuth oxide, 2 parts of sodium dibutylnaphthalenesulfonate, 0.2 parts of sodium polyacrylate, and 250 parts of soft water; 180 parts of erbium oxide, 1 part of sodium dibutylnaphthalenesulfonate, and 180 parts of soft water; 155 parts of tin oxide, 1 part of sodium dibutylnaphthalenesulfonate, and 160 parts of soft water. The planetary ball mill was operated at a speed of 300 rpm, and the ball milling time was 18 hours to obtain the corresponding shielding filler dispersion.

[0041] (2.2) Preparation of pre-made rubber emulsion: 100 parts of dry rubber content of 60% natural latex, 1.5 parts of sulfur, 1.5 parts of zinc diethyl dithiocarbamate, 1 part of zinc oxide, 0.3 parts of N-isopropyl-N'-phenyl-p-phenylenediamine, 0.1 parts of sodium methylene bis-naphthalene sulfonate, 0.5 parts of potassium hydroxide, 0.15 parts of sodium polyacrylate, were stirred at a speed of 300 rpm for 60 minutes at room temperature, and then left to stand for 24 hours. After filtration, a pre-made natural rubber emulsion was obtained. (2.3) The shielding filler dispersion liquid prepared in step (2.1) was added to the pre-made rubber emulsion in step (2.2), and stirred at a speed of 500 rpm for 120 minutes. After standing and filtration, a natural rubber compounding emulsion containing shielding fillers was obtained.

[0042] (3) Preparation of rubber products with self-cleaning and radiation protection functions (3.1) The clean mold was immersed in a 10% calcium chloride solution, the solution temperature was 60 ℃, the mold was taken out after 10 seconds of immersion, and the mold was dried in an oven at a temperature of 120 ℃. The dried mold was taken out after 5 minutes and naturally cooled to room temperature.

[0043] (3.2) The natural rubber compounding emulsion containing tin oxide, erbium oxide and bismuth oxide was immersed in turn, and the temperature of the above emulsion was 35 ℃. The mold was taken out at a uniform speed of 15 cm / min after 5 seconds of immersion. The mold was dried at 75 ℃ for 30 minutes, and the immersion was repeated until the thickness of the shielding single layer containing tin oxide was 0.65 mm, the thickness of the shielding single layer containing erbium oxide was 0.85 mm, and the thickness of the shielding single layer containing bismuth oxide was 1.5 mm.

[0044] (3.3) The mold in step (3.2) was dried at 90 ℃ for 40 minutes to completely shape the rubber product, and then talcum powder was evenly applied on the surface of the rubber product for demolding. After demolding, the rubber product was cooked in boiling water at 100 ℃ for 60 minutes, then taken out and cleaned, and finally dried at 60 ℃ for 30 minutes.

[0045] (3.4) The suspension solution of 100 ml used for the self-cleaning layer in step 1 was loaded into an airbrush, and sprayed back and forth 8 times at a pressure of 0.25 MPa and a distance of 15 cm from the side of the shielding layer containing bismuth oxide in step (2.3). Then, the product was dried at 120 ℃ for 10 minutes to obtain a natural rubber protective product with self-cleaning ability.

[0046] The source used was 241 When the Am source was used, the shielding rate of the 3 mm thick product in this example to γ-rays was 75.3%, and the contact angle of the self-cleaning layer was 162° and the rolling angle was 3°. The rubber product in this example had good γ-ray shielding performance and self-cleaning ability.

[0047] Example 2 (1) Preparation of the suspension for the self-cleaning layer On the basis of Example 1, a 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane solution with a concentration of 10% was additionally prepared, with anhydrous ethanol as the solvent.

[0048] (2) Preparation of the rubber compounding emulsion for the neutron shielding single layer (2.1) Ball milling of the shielding filler: the corresponding neutron shielding filler was ball milled according to the following composition: 50 parts of boron carbide, 0.3 parts of sodium dibutylnaphthalenesulfonate, 60 parts of soft water; 40 parts of boron nitride, 0.3 parts of sodium dibutylnaphthalenesulfonate, 60 parts of soft water; 45 parts of lithium chloride, 0.2 parts of sodium dibutylnaphthalenesulfonate, 50 parts of soft water; 20 parts of gadolinium boride, 0.1 parts of sodium dibutylnaphthalenesulfonate, 25 parts of soft water. The planetary ball mill was operated at a speed of 300 rpm for 24 hours to obtain the corresponding shielding filler dispersion.

[0049] (2.2) Preparation of the pre-rubber emulsion: at room temperature, 100 parts of dry rubber with a dry rubber content of 49% carboxyl styrene-butadiene latex, 2 parts of sulfur, 2.5 parts of zinc diethyl dithiocarbamate, 3 parts of zinc oxide, 0.1 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 0.1 parts of sodium methylene bisnaphthalenesulfonate, 0.5 parts of potassium hydroxide, 1 parts of casein, 0.2 parts of sodium polyacrylate, were stirred at a speed of 300 rpm for 60 minutes, and then left to stand for 24 hours. After filtration, the pre-carboxyl styrene-butadiene emulsion was obtained. (2.3) The shielding filler dispersion prepared in step (2.1) was added to the pre-rubber emulsion in step (2.2), and stirred at a speed of 500 rpm for 120 minutes. After standing and filtration, the carboxyl styrene-butadiene compounding emulsion containing the shielding filler was obtained.

[0050] (3) Preparation of rubber products with self-cleaning and radiation protection functions (3.1) The clean mold was immersed in a 20% calcium chloride solution, the solution temperature was 60 ℃, the mold was taken out after 10 seconds of immersion, and the mold was dried in an oven at a temperature of 120 ℃. The mold was taken out after 5 minutes and naturally cooled to room temperature.

[0051] (3.2) The carboxyl styrene-butadiene compounding emulsion containing boron carbide, boron nitride, lithium chloride, and gadolinium boride was sequentially immersed, and the temperature of the above emulsion was 35 ℃. The mold was taken out at a uniform speed of 10 cm / min after 10 seconds of immersion, and dried at 80 ℃ for 30 minutes. The immersion was repeated until the thickness of the shielding single layer containing boron carbide was 6 mm, the thickness of the shielding single layer containing boron nitride was 4 mm, the thickness of the shielding single layer containing lithium chloride was 4 mm, and the thickness of the shielding single layer containing gadolinium boride was 1 mm.

[0052] (3.3) Dry the mold in step (3.2) at 105 °C for 60 minutes to completely shape the rubber product, then evenly apply talcum powder on the surface for demolding, and after demolding, cook in boiling water at 100 °C for 90 minutes, and after taking out, clean and dry at 60 °C for 30 minutes.

[0053] (3.4) Immerse the rubber product in step (3.3) in the suspension solution for the self-cleaning layer, with the temperature of the suspension solution being room temperature, and the immersion time being 10 seconds, and then dry at 120 °C for 10 minutes.

[0054] (3.5) After plasma treatment for 10 minutes, immerse the rubber product in step (3.4) in a 10% 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane solution for 10 seconds, and then take out the rubber product and dry naturally at room temperature to obtain the finished carboxylated styrene-butadiene rubber protective product with self-cleaning ability.

[0055] The radiation source used is 252 When the Cf neutron source is used, the shielding rate of the 15 mm thick product in this embodiment is 51.6% for fast neutrons, 65.8% for medium-energy neutrons, and 78.5% for slow neutrons, the contact angle of the self-cleaning layer is 158°, and the rolling angle is 5°. The carboxylated styrene-butadiene rubber in this embodiment has good anti-radiation aging performance and good γ-ray shielding performance and self-cleaning ability.

[0056] Example 3 In this embodiment, the self-cleaning layer is the same as in Example 1, the layer structure and formula of the γ-ray shielding layer are the same as in Example 1, and the layer structure and formula of the neutron shielding layer are the same as in Example 2. The only difference is that the thickness of each single layer is different from that in Examples 1 and 2, specifically: The thickness of the tin oxide layer is 0.65 mm; the thickness of the erbium oxide layer is 0.85 mm; the thickness of the bismuth oxide layer is 1.5 mm; the thickness of the boron carbide layer is 1 mm; the thickness of the boron nitride layer is 0.45 mm; the thickness of the lithium chloride layer is 0.35 mm; and the thickness of the gadolinium boride layer is 0.2 mm.

[0057] In this embodiment, the shielding rate of the 5 mm thick product is 241 The shielding rate of the γ-ray from the Am source is 76.8%, the shielding rate of the reactor thermal neutron source (neutron energy is 0.025 eV) is 85.6%, the contact angle of the self-cleaning layer is 162°, and the rolling angle is 3°. The rubber product in this embodiment has good γ-ray shielding performance and self-cleaning ability.

[0058] Comparative Example 1 The difference from Example 1 is that the natural rubber compounding emulsion containing tin oxide, bismuth oxide and erbium oxide is sequentially dipped. The shielding rate of the product of 3 mm thickness against γ-rays is 69.4% unlike Example 1.

[0059] Comparative Example 2 The difference from Example 1 is that the natural rubber compounding emulsion containing erbium oxide, tin oxide and bismuth oxide is sequentially dipped. The shielding rate of the product of 3 mm thickness against γ-rays is 72.5% unlike Example 1.

[0060] Comparative Example 3 The difference from Example 1 is that the natural rubber compounding emulsion containing erbium oxide, bismuth oxide and tin oxide is sequentially dipped. The shielding rate of the product of 3 mm thickness against γ-rays is 70.5% unlike Example 1.

[0061] Comparative Example 4 The difference from Example 1 is that the natural rubber compounding emulsion containing bismuth oxide, tin oxide and erbium oxide is sequentially dipped. The shielding rate of the product of 3 mm thickness against γ-rays is 71.1% unlike Example 1.

[0062] Comparative Example 5 The difference from Example 1 is that the natural rubber compounding emulsion containing bismuth oxide, erbium oxide and tin oxide is sequentially dipped. The shielding rate of the product of 3 mm thickness against γ-rays is 69.6% unlike Example 1.

[0063] Comparative Example 6 The difference from Example 2 is that the carboxylated styrene butadiene compounding emulsion containing boron carbide, boron nitride, gadolinium boride and lithium chloride is sequentially dipped. Unlike Example 2, the radiation source used is 252 Cf neutron source, the shielding rate of the product of 15 mm thickness against fast neutrons is 48.3%, against medium energy neutrons is 58.7% and against slow neutrons is 72.1%.

[0064] Comparative Example 7 The difference from Example 2 is that the carboxylated styrene butadiene compounding emulsion containing boron carbide, lithium chloride, boron nitride and gadolinium boride is sequentially dipped. Unlike Example 2, the radiation source used is 252 Cf neutron source, the shielding rate of the product of 15 mm thickness against fast neutrons is 45.1%, against medium energy neutrons is 62.4% and against slow neutrons is 69.5%.

[0065] Comparative Example 8 The difference from Example 2 is that the carboxylated styrene butadiene compounding emulsion containing boron carbide, lithium chloride, gadolinium boride and boron nitride is sequentially dipped. Unlike Example 2, the radiation source used is252 The 15 mm thick article in this example had a shielding efficiency of 49.7% for fast neutrons, 56.9% for intermediate energy neutrons, and 75.2% for slow neutrons when exposed to a Cf neutron source.

[0066] Comparative Example 9 The difference between this example and Example 2 is that the carboxylic styrene butadiene latex emulsion was sequentially immersed with boron carbide, gadolinium boride, boron nitride, and lithium chloride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article in this example had a shielding efficiency of 43.6% for fast neutrons, 64.1% for intermediate energy neutrons, and 71.8% for slow neutrons when exposed to a Cf neutron source.

[0067] Comparative Example 10 The difference between this example and Example 2 is that the carboxylic styrene butadiene latex emulsion was sequentially immersed with boron carbide, gadolinium boride, lithium chloride, and boron nitride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article in this example had a shielding efficiency of 47.2% for fast neutrons, 59.3% for intermediate energy neutrons, and 76.4% for slow neutrons when exposed to a Cf neutron source.

[0068] Comparative Example 11 The difference between this example and Example 2 is that the carboxylic styrene butadiene latex emulsion was sequentially immersed with boron nitride, boron carbide, lithium chloride, and gadolinium boride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article in this example had a shielding efficiency of 42.8% for fast neutrons, 61.5% for intermediate energy neutrons, and 73.9% for slow neutrons when exposed to a Cf neutron source.

[0069] Comparative Example 12 The difference between this example and Example 2 is that the carboxylic styrene butadiene latex emulsion was sequentially immersed with boron nitride, boron carbide, gadolinium boride, and lithium chloride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article in this example had a shielding efficiency of 44.9% for fast neutrons, 57.2% for intermediate energy neutrons, and 74.6% for slow neutrons when exposed to a Cf neutron source.

[0070] Comparative Example 13 The difference between this example and Example 2 is that the carboxylic styrene butadiene latex emulsion was sequentially immersed with boron nitride, lithium chloride, boron carbide, and gadolinium boride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article in this example had a shielding efficiency of 48.6% for fast neutrons, 60.4% for intermediate energy neutrons, and 70.3% for slow neutrons when exposed to a Cf neutron source.

[0071] Comparative Example 14 Example 2 except that the carboxy styrene emulsion was sequentially immersed in boron nitride, lithium chloride, gadolinium boride and boron carbide. As in Example 2, the radiation source used was a Cf neutron source. 252 When the Cf neutron source was used, the 15 mm thick article of this example had a fast neutron shielding of 42.1%, a medium energy neutron shielding of 55.9% and a slow neutron shielding of 77.0%.

[0072] Comparative Example 15 Example 2 except that the carboxy styrene emulsion was sequentially immersed in boron nitride, lithium chloride, gadolinium boride and boron carbide. As in Example 2, the radiation source used was a Cf neutron source. 252 When the Cf neutron source was used, the 15 mm thick article of this example had a fast neutron shielding of 42.1%, a medium energy neutron shielding of 55.9% and a slow neutron shielding of 77.0%.

[0073] Comparative Example 16 Example 2 except that the carboxy styrene emulsion was sequentially immersed in boron nitride, lithium chloride, gadolinium boride and boron carbide. As in Example 2, the radiation source used was a Cf neutron source. 252 When the Cf neutron source was used, the 15 mm thick article of this example had a fast neutron shielding of 42.1%, a medium energy neutron shielding of 55.9% and a slow neutron shielding of 77.0%.

[0074] Comparative Example 17 Example 2 except that the carboxy styrene emulsion was sequentially immersed in boron nitride, lithium chloride, gadolinium boride and boron carbide. As in Example 2, the radiation source used was a Cf neutron source. 252 When the Cf neutron source was used, the 15 mm thick article of this example had a fast neutron shielding of 42.1%, a medium energy neutron shielding of 55.9% and a slow neutron shielding of 77.0%.

[0075] Comparative Example 18 Example 2 except that the carboxy styrene emulsion was sequentially immersed in boron nitride, lithium chloride, gadolinium boride and boron carbide. As in Example 2, the radiation source used was a Cf neutron source. 252 When the Cf neutron source was used, the 15 mm thick article of this example had a fast neutron shielding of 42.1%, a medium energy neutron shielding of 55.9% and a slow neutron shielding of 77.0%.

[0076] Comparative Example 19 Example 2 except that the carboxy styrene emulsion was sequentially immersed in boron nitride, lithium chloride, gadolinium boride and boron carbide. As in Example 2, the radiation source used was a Cf neutron source. 252The 15 mm thick article of this example had a shielding efficiency of 47.8% for fast neutrons, 56.3% for intermediate energy neutrons, and 73.4% for slow neutrons when exposed to a Cf neutron source.

[0077] Comparative Example 20 The difference between this example and Example 2 is that the carboxystyrene emulsion was sequentially immersed in lithium chloride, gadolinium boride, boron carbide, and boron nitride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article of this example had a shielding efficiency of 46.0% for fast neutrons, 61.0% for intermediate energy neutrons, and 76.9% for slow neutrons when exposed to a Cf neutron source.

[0078] Comparative Example 21 The difference between this example and Example 2 is that the carboxystyrene emulsion was sequentially immersed in lithium chloride, gadolinium boride, boron nitride, and boron carbide. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article of this example had a shielding efficiency of 44.2% for fast neutrons, 63.5% for intermediate energy neutrons, and 70.6% for slow neutrons when exposed to a Cf neutron source.

[0079] Comparative Example 22 The difference between this example and Example 2 is that the carboxystyrene emulsion was sequentially immersed in gadolinium boride, boron carbide, boron nitride, and lithium chloride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article of this example had a shielding efficiency of 48.0% for fast neutrons, 59.6% for intermediate energy neutrons, and 74.1% for slow neutrons when exposed to a Cf neutron source.

[0080] Comparative Example 23 The difference between this example and Example 2 is that the carboxystyrene emulsion was sequentially immersed in gadolinium boride, boron carbide, lithium chloride, and boron nitride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article of this example had a shielding efficiency of 42.5% for fast neutrons, 57.8% for intermediate energy neutrons, and 72.8% for slow neutrons when exposed to a Cf neutron source.

[0081] Comparative Example 24 The difference between this example and Example 2 is that the carboxystyrene emulsion was sequentially immersed in gadolinium boride, boron nitride, boron carbide, and lithium chloride. The difference between this example and Example 2 is that the radiation source used was 252 The 15 mm thick article of this example had a shielding efficiency of 49.5% for fast neutrons, 60.8% for intermediate energy neutrons, and 68.2% for slow neutrons when exposed to a Cf neutron source.

[0082] Comparative Example 25 The difference from Example 2 is that the carboxy styrene emulsion containing gadolinium boride, boron nitride, lithium chloride and boron carbide is sequentially immersed. The difference from Example 2 is that the radiation source used is 252 When the Cf neutron source is used, the shielding rate of the 15 mm thick product in this example to fast neutrons is 45.4%, to medium energy neutrons is 64.5%, and to slow neutrons is 75.0%.

[0083] Comparative Example 26 The difference from Example 2 is that the carboxy styrene emulsion containing gadolinium boride, lithium chloride, boron carbide and boron nitride is sequentially immersed. The difference from Example 2 is that the radiation source used is 252 When the Cf neutron source is used, the shielding rate of the 15 mm thick product in this example to fast neutrons is 47.5%, to medium energy neutrons is 55.1%, and to slow neutrons is 71.5%.

[0084] Comparative Example 27 The difference from Example 2 is that the carboxy styrene emulsion containing gadolinium boride, lithium chloride, boron nitride and boron carbide is sequentially immersed. The difference from Example 2 is that the radiation source used is 252 When the Cf neutron source is used, the shielding rate of the 15 mm thick product in this example to fast neutrons is 43.0%, to medium energy neutrons is 62.0%, and to slow neutrons is 69.1%.

[0085] Comparative Example 28 The difference from Example 2 is that the carboxy styrene emulsion containing boron nitride, gadolinium boride, boron carbide and lithium chloride is sequentially immersed. The difference from Example 2 is that the radiation source used is 252 When the Cf neutron source is used, the shielding rate of the 15 mm thick product in this example to fast neutrons is 46.5%, to medium energy neutrons is 63.8%, and to slow neutrons is 68.7%.

[0086] Comparative Example 29 The difference from Example 3 is that the position relationship of the exchanged gamma ray shielding layer and the neutron shielding layer is changed.

[0087] The shielding rate of the product after 5 mm in this comparative example to 241 The shielding rate to the gamma ray of the Am source is 70.5%, and the shielding rate to the reactor thermal neutron source (neutron energy is 0.025 eV) is 76.3%.

[0088] The above only describes the preferred embodiments of the present application and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A rubber product with self-cleaning and radiation protection functions, the radiation source being: 241 gamma rays in Am source and / or 252 Cf neutron source and / or reactor thermal neutron source, characterized in that, The rubber product comprises: an optional gamma ray shielding layer, an optional neutron shielding layer, a self-cleaning layer arranged in turn from inside to outside; at least one of the gamma ray shielding layer and the neutron shielding layer is arranged; the gamma ray shielding layer and the neutron shielding layer are both multi-layer structures; The gamma ray shielding layer comprises a tin oxide layer, an erbium oxide layer, and a bismuth oxide layer arranged in turn from inside to outside; The neutron shielding layer comprises a boron carbide layer, a boron nitride layer, a lithium chloride layer, and a gadolinium boride layer arranged in turn from inside to outside; Each layer inside the neutron shielding layer and the gamma ray shielding layer is formed by dispersing shielding fillers of tin oxide, erbium oxide, bismuth oxide, boron carbide, boron nitride, lithium chloride, or gadolinium boride in a shielding filler dispersion liquid, and then mixing the shielding filler dispersion liquid with rubber latex and compounding agents, and drying the mixture to obtain; The self-cleaning layer is formed by spraying or dipping a self-cleaning material.

2. The rubber product with self-cleaning and radiation protection functions according to claim 1, wherein The rubber latex comprises one or more of natural latex, styrene-butadiene latex, carboxyl styrene-butadiene latex, polyurethane latex, chloroprene latex, nitrile-butadiene latex, ethylene-propylene latex, butyl latex, and chlorosulfonated polyethylene latex.

3. The rubber product with self-cleaning and radiation protection functions according to claim 1, wherein In a single layer of the gamma ray shielding layer, 100 parts by weight of rubber latex, 4-50 parts by weight of compounding agents, and 30-500 parts of gamma ray shielding fillers are used based on dry rubber. In a single layer of the neutron shielding layer, 100 parts by weight of rubber latex, 4-50 parts by weight of compounding agents, and 20-500 parts of neutron shielding fillers are used based on dry rubber. The compounding agents comprise one or more of 0.5-7 parts by weight of vulcanizing agents, 0.5-15 parts by weight of accelerators, 1-20 parts by weight of active agents, 0.1-5 parts by weight of anti-aging agents, 0.1-4 parts by weight of dispersants, 0.1-3 parts by weight of stabilizers, and 0.001-2 parts by weight of thickening agents.

4. The rubber product with self-cleaning and radiation protection functions according to claim 3, wherein The vulcanizing agent is sulfur and / or 4,4'-dithiodimorpholine; The accelerator is zinc diethyl dithiocarbamate and / or zinc ethyl phenyl dithiocarbamate; The active agent is zinc oxide and / or zinc carbonate; The anti-aging agent used is one or more of N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl ester, N-isopropyl-N'-phenyl-p-phenylenediamine, and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine; The dispersant is sodium methylene dithiophenyl sulfonate and / or potassium pyrophosphate; The stabilizer is casein and / or potassium hydroxide; The thickening agent is one or more of sodium polyacrylate, ammonium polymethacrylate, methyl cellulose, sodium alginate, and hydroxyethyl cellulose.

5. The rubber article having self-cleaning and radiation protection functions according to claim 1, wherein, The particle size of the shielding fillers of tin oxide, erbium oxide, bismuth oxide, boron carbide, boron nitride, lithium chloride, or gadolinium boride ranges from 0.02 to 50 μm.

6. The rubber article having self-cleaning and radiation protection functions according to claim 1, wherein, The raw material quality composition of the self-cleaning layer comprises 3%-20% polydimethylsiloxane, 1%-12% solid particles, 60.5%-92% organic solvent, 0.3%-6% crosslinking agent, and 0.1%-1.5% catalyst.

7. The rubber product with self-cleaning and radiation protection functions according to claim 6, wherein, The solid particles comprise one or more of silicon dioxide, graphene, carbon nanotubes, and carbon black; The mass ratio of the solid particles with a particle size in the micron level to the solid particles with a particle size in the nanometer level is 100:15-25; The organic solvent comprises one or more of ethanol, isopropyl alcohol, acetone, n-hexane, cyclohexane, and tetrahydrofuran; The crosslinking agent comprises one or more of polybutadiene, tetraethyl orthosilicate, perfluoroalkyl ethyl trimethoxysilane, and hexamethyldisilazane; The catalyst comprises one or more of tert-butyl peroxybenzoate, dibutyltin dilaurate, diazabicycloundecane, and tetraisopropyl titanate.

8. The rubber product with self-cleaning and radiation protection functions according to claim 1, wherein, The thickness of the tin oxide layer is 0.4-1.2 mm; The thickness of the erbium oxide layer is 0.6-1.5 mm; The thickness of the bismuth oxide layer is 1-2.2 mm; The thickness of the boron carbide layer is 0.5-8 mm; The thickness of the boron nitride layer is 0.1-6 mm; The thickness of the lithium chloride layer is 0.1-6 mm; The thickness of the gadolinium boride layer is 0.1-1.5 mm.

9. The rubber product with self-cleaning and radiation protection functions according to claim 8, wherein, The thickness of the tin oxide layer is 0.6-0.7 mm; The thickness of the erbium oxide layer is 0.8-0.9 mm; The thickness of the bismuth oxide layer is 1.4-1.6 mm; The thickness of the boron carbide layer is 0.8-6.5 mm; The thickness of the boron nitride layer is 0.2-4.5 mm; The thickness of the lithium chloride layer is 0.2-4.5 mm; The thickness of the gadolinium boride layer is 0.15-1.1 mm.

10. The method of producing a rubber product having self-cleaning and radiation protection functions according to any one of claims 1 to 9, characterized in that, The preparation method comprises: forming a gamma ray shielding layer and / or a neutron shielding layer on a mold in sequence by a dipping process; the gamma ray shielding layer comprises a tin oxide layer, an erbium oxide layer, and a bismuth oxide layer in sequence; the neutron shielding layer comprises a boron carbide layer, a boron nitride layer, a lithium chloride layer, and a gadolinium boride layer in sequence; drying and demolding; forming a self-cleaning layer by a spraying or dipping process; drying to obtain the rubber product with self-cleaning and radiation protection functions.

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