CN114591573A - Sealing rubber, preparation method thereof and sealing capsule - Google Patents
Sealing rubber, preparation method thereof and sealing capsule Download PDFInfo
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- CN114591573A CN114591573A CN202210286525.0A CN202210286525A CN114591573A CN 114591573 A CN114591573 A CN 114591573A CN 202210286525 A CN202210286525 A CN 202210286525A CN 114591573 A CN114591573 A CN 114591573A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention provides sealing rubber, a preparation method thereof and a sealing capsule, wherein the preparation method of the sealing rubber comprises the following steps: plasticating or hot-smelting 80-120 parts of ethylene propylene diene monomer rubber by mass to obtain a main body material; mixing the main body material with 10-30 parts of an active agent, 30-60 parts of a reinforcing agent, 30-60 parts of a softening agent and 30-90 parts of a radiation-resistant filler for one time, and uniformly dispersing to obtain a large material; and after the large material is placed, mixing the large material with 3-15 parts of accelerator and 0.5-2 parts of vulcanizing agent for the second time, and dispersing uniformly to obtain the sealing rubber. The sealing rubber comprises the sealing rubber prepared by the preparation method of the sealing rubber. The sealing capsule is made of the sealing rubber prepared by the preparation method of the sealing rubber. The sealing rubber has the advantages that the sealing rubber is long in service life and high in safety performance, and the manufactured safety sealing capsule is easy to install and has the characteristics of high rebound resilience, air inflation performance, stability and durability.
Description
Technical Field
The invention relates to the technical field of door seals in nuclear power steam generator maintenance, in particular to a sealing rubber, a preparation method thereof and a sealing capsule.
Background
At present, the steam generator blocking plate technology is monopolized abroad, the technology is related in China but the manufacturing of a key part capsule of the blocking plate is not overcome, and the steam generator blocking plate adopted in nuclear power generating units in service and under construction in China mainly depends on import. The closure plate component comprises a middle plate, a side plate, a sealing air bag and a fastener, the other parts except the sealing air bag can be recycled, but the whole component is purchased at foreign countries at present, the price is high, the delivery period is long, and therefore the closure plate component is limited by the 'neck of a card' in the United states for a long time. In the operation process of the nuclear power station, a nuclear power station owner needs to send related operators to a product producing country for training besides purchasing the closure plate product. If an accident happens, a corresponding manufacturer is required to go to the site for repair, and the delayed time causes great economic loss to the delay of the maintenance work of the nuclear power plant.
In order to promote the localization process of the nuclear power technology supporting equipment in China and improve the reliability, economy and convenience of the subsequent nuclear power station refueling and maintenance process and the periodic maintenance of the nuclear power station evaporator, it is necessary to develop the design research of the primary side plugging plate sealing capsule of the nuclear power station steam generator. The factors such as the reliability of equipment, the economical efficiency of engineering, the convenience of maintenance work and the like are comprehensively considered by a team, the developed, produced and tested steam generator primary side plugging plate sealing capsule can be directly applied to the third-generation nuclear power project of China, and the related test conditions can also provide references for the design and improvement of steam generator plugging plates of other nuclear power stations.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, an object of the present invention is to provide a sealing rubber with a long service life, high stability and strong radiation resistance, a preparation method thereof, and a sealing capsule.
The invention provides a preparation method of sealing rubber, which comprises the following steps:
plasticating or hot-smelting 80-120 parts of ethylene propylene diene monomer rubber by mass to obtain a main body material;
mixing the main body material with 10-30 parts of an active agent, 30-60 parts of a reinforcing agent, 30-60 parts of a softening agent and 30-90 parts of a radiation-resistant filler for one time, and uniformly dispersing to obtain a large material;
and after the large material is placed, mixing the large material with 3-15 parts of accelerator and 0.5-2 parts of vulcanizing agent for the second time, and dispersing uniformly to obtain the sealing rubber.
In an exemplary embodiment of the present invention, the preparation method may further include:
before secondary mixing, the large materials are subjected to heat refining so as to be beneficial to adding materials;
and refining the sealing rubber after secondary mixing to improve the dispersion uniformity of each component and the main material.
In an exemplary embodiment of the invention, the active agent may include: zinc oxide, stearic acid and a silane coupling agent;
wherein, in the activating agent, the mass percentage of zinc oxide can be 30-50%, the mass percentage of stearic acid can be 3-10%, and the mass percentage of silane coupling agent can be 30-50%.
In an exemplary embodiment of the present invention, the reinforcing agent may be highly abrasion-resistant carbon black, the softening agent may be paraffin oil, and the vulcanizing agent may be sulfur.
In an exemplary embodiment of the present invention, the radiation resistant filler may include: bismuth trioxide, nano barite and rare earth gadolinium oxide;
in the anti-radiation filler, the mass ratio of the bismuth trioxide can be 20-50%, the mass ratio of the nano barite can be 20-50%, and the mass ratio of the rare earth gadolinium oxide can be 20-50%.
In an exemplary embodiment of the present invention, the promoter may include: TBZTD, CZ, DM, DTDC and BZ;
in the accelerant, the mass proportion of TBZTD can be 20-35%, the mass proportion of CZ can be 20-35%, the mass proportion of DM can be 10-20%, the mass proportion of DTDC can be 10-20%, and the mass proportion of BZ can be 10-20%.
In an exemplary embodiment of the present invention, the temperature of the plastication or mastication may be 120 to 140 ℃, the time may be 3 to 5min, and the pressure may be 0.3 to 1.0 Mpa.
In an exemplary embodiment of the present invention, the temperature of the primary mixing and the secondary mixing may be 130 to 150 ℃, the time may be 8 to 25min, and the pressure may be 0.3 to 1.0 Mpa.
In another aspect, the present invention provides a sealing rubber, which may include a sealing rubber prepared by the preparation method according to any one of the above exemplary embodiments.
In still another aspect, the present invention provides a sealing capsule which may be made of the sealing rubber as described in the above exemplary embodiments.
Compared with the prior art, the beneficial effects of the invention can comprise at least one of the following:
(1) the formula of the invention has long service life, and has the characteristics of radiation and aging resistance, strong acid resistance, small specific gravity, tear resistance, strong bursting resistance and the like;
(2) the sealed capsule has the characteristics of high resilience and air inflation, stability, durability, easy installation and the like.
Detailed Description
Hereinafter, the sealing rubber of the present invention, the production method thereof, and a sealed capsule will be described in detail with reference to exemplary embodiments.
It should be noted that "first," "second," and the like are merely for convenience of description and for ease of distinction, and are not to be construed as indicating or implying relative importance. "upper," "lower," "inner," and "outer" are merely for convenience of description and relative orientation or positional relationship, and do not indicate or imply that the referenced components must have that particular orientation or position.
In a first exemplary embodiment of the present invention, the sealing rubber preparation method includes:
s1: adding 80-120 parts by mass of Ethylene Propylene Diene Monomer (EPDM) into an internal rubber mixing mill for plastication or thermal mixing to obtain a main material. For example, the ethylene propylene diene monomer may be 85, 96, 102, 115 parts. Here, the EPDM rubber has excellent properties of ozone resistance, heat resistance, chemical resistance and the like because the main chain is composed of chemically stable saturated hydrocarbons and contains only unsaturated double bonds in the side chains, and can be used as a main raw material for preparing sealing rubber.
S2: and continuously adding 10-30 parts of activator, 30-60 parts of reinforcing agent, 30-60 parts of softener and 30-90 parts of anti-radiation filler into an internal rubber mixing mill, and carrying out primary mixing and uniform dispersion to obtain the coarse material. For example, the active agent is added in the amount of 10.4, 23.6 and 29.0 parts; the adding amount of the reinforcing agent is 34.6, 55.6 and 59.0 parts; the adding amount of the softener is 34.6, 55.6 and 59.0 parts; the dosage of the radiation-resistant filler is 32.2, 43.6, 60.4, 74.5, 87.1 and 88.7 parts. And (4) carrying out sheet discharging and standing for 24 hours on the large materials.
S3: and adding 3-15 parts of accelerator, 0.5-2 parts of vulcanizing agent and the large material into an open rubber mixing mill for secondary mixing and uniformly dispersing to obtain the sealing rubber.
In this embodiment, the active agent component includes zinc oxide, stearic acid, and a silane coupling agent. In the activating agent, the mass ratio of zinc oxide is 30-50%, the mass ratio of stearic acid is 3-10%, and the mass ratio of silane coupling agent is 30-50%. The zinc oxide reacts with the accelerator in the EPDM matrix to generate a complex, further promotes the decomposition of the vulcanizing agent, and reacts with unsaturated double bonds of EPDM side chains to generate a three-dimensional network structure, so that the rubber is endowed with excellent service performance, the vulcanization time is shortened, and the rubber is energy-saving and environment-friendly. Stearic acid can activate the surface of zinc oxide, more accelerator reacts with zinc oxide, and the above decomposition and reaction processes are repeated. For example, the active agent may include, in parts by mass: 5-10 parts of silane coupling agent, such as 6.4, 7.0, 8.6 and 9.3 parts; 5-10 parts of zinc oxide, such as 6.4, 7.0, 8.6 and 9.3 parts; 1-3 parts of stearic acid, such as 1.5, 1.9, 2.2 and 2.8 parts.
In this embodiment, the reinforcing agent may be highly abrasion resistant carbon black. Here, EPDM is a non-self-reinforcing rubber, which has low self-strength and needs to be reinforced with carbon black to improve its mechanical properties. The high wear-resistant furnace black N330 with small particle size, high oil absorption and iodine absorption values and large specific surface area is selected as the reinforcing agent, so that the EPDM (ethylene-propylene-diene monomer) can be endowed with excellent mechanical property and can resist the physical damage of the flexible sealing material caused in the stretching or compressing process.
In this embodiment, the softening agent may be paraffin oil. Here, the refined 500# paraffin oil becomes chain saturated aliphatic hydrocarbon, has high kinematic viscosity and excellent compatibility with EPDM, and does not precipitate on the surface of the flexible sealing material to influence the use performance of the material. Secondly, it can lubricate during processing and improve the dispersivity of N330 in EPDM.
In this embodiment, the vulcanizing agent may be sulfur. For example, the vulcanizing agent can be barium sulfate, and the adding content is 10-30 parts. For example, 12, 15, 18 parts. In this embodiment, the temperature of the plastication or mastication in step S1 is 120 to 140 ℃, for example, 123, 134, 137 ℃; the time is 3-5 min, such as 3.2, 4.2 and 4.7 min; the pressure is 0.3 to 1.0MPa, for example, 0.36, 0.47, 0.68, 0.92 MPa. The temperature of the first mixing and the second mixing is 130-150 ℃, such as 134, 145 and 147 ℃; the time is 8-25 min, such as 9.6, 14.2, 16.0 and 23.5 min. The pressure is 0.3 to 1.0MPa, for example, 0.36, 0.47, 0.68, 0.92 MPa.
In the present embodimentThe radiation-resistant filler comprises bismuth trioxide, barium sulfate and gadolinium trioxide. The radiation-resistant filler comprises the following components in parts by weight: 10-30 parts of bismuth trioxide, 10-30 parts of gadolinium trioxide and 10-30 parts of barium sulfate. Here, the conventional X-ray shielding material is mainly lead, but on the one hand, lead is highly toxic, and on the other hand, element Bi has a mass attenuation coefficient nearly identical to that of Pb, that is, Bi has an X-ray shielding function equivalent to that of Pb. Therefore, Bi is selected for use in the present application2O3As a substitute functional material of PbO, the toxicity of the X-ray shielding material is avoided. Barite is a nonmetallic mineral with barium sulfate as the main component, has stable chemical property, and is easy to absorb X rays and gamma rays. And the barite is a natural mineral, the reserves are very abundant, can obtain the high-purity product after purifying, the processing technology is simple, with low costs, pollute little. The traditional elements for absorbing thermal neutrons include boron, lithium, cadmium, rare earth and the like, wherein gadolinium contained in the rare earth has the highest thermal neutron capture cross section, and a gadolinium-containing polymer is an ideal neutron shielding material. Wherein, in the anti-radiation filler, the mass ratio of the bismuth trioxide is 20-50%, the mass ratio of the nano barite is 20-50%, and the mass ratio of the rare earth gadolinium oxide is 20-50%. In the embodiment, in the accelerant, the mass ratio of TBZTD is 20-35%, the mass ratio of CZ is 20-35%, the mass ratio of DM is 10-20%, the mass ratio of DTDC is 10-20%, and the mass ratio of BZ is 10-20%. Wherein, the mass parts of the components of the accelerant in each hundred parts of the rubber matrix are as follows: TBZTD 1-3 parts, such as 1.2, 2.4, 2.7 parts; 1-3 parts of CZ, such as 1.2, 2.4 and 2.7 parts; DM 0.5-2 parts, such as 0.5, 1.3, 1.9 parts; 0.5-2 parts of DTDC, such as 0.5, 1.3 and 1.9 parts; 0.5-2 parts of BZ, such as 0.5, 1.3 and 1.9 parts. In this embodiment, the step of mixing and uniformly dispersing in S2 includes the following steps:
s21: mixing and uniformly dispersing a silane coupling agent, zinc oxide, stearic acid and a main material, wherein the mixing and dispersing temperature is 130-150 ℃ in S21, such as 132 ℃, 146 ℃ and 148 ℃; the time is 2-5 min, such as 2.4, 4.5, 5.0min, and the pressure is 0.6-1.0 MPa, such as 0.7MPa, 0.8MPa, 0.9 MPa. S21, mixing and uniformly dispersing the main material and the activator, which is helpful for activating a formula vulcanization system and increasing the network density of rubber molecules; s22: mixing and uniformly dispersing paraffin oil, high abrasion furnace carbon black and a product of S21, wherein the mixing and dispersing temperature is 130-150 ℃ in S22, such as 132, 146 and 148 ℃; the time is 6-10 min, such as 6.3, 8.2, 9.5min, and the pressure is 0.6-1.0 MPa, such as 0.7MPa, 0.8MPa, 0.9 MPa; s23: the filler and the product of S22 were kneaded and uniformly dispersed to obtain a large material. In S23, the mixing and dispersing temperature is 130-150 ℃, such as 132, 146 and 148 ℃; the time is 6-10 min, such as 6.3, 8.2, 9.5min, and the pressure is 0.6-1.0 MPa, such as 0.7MPa, 0.8MPa, 0.9 MPa.
In this embodiment, the large material blanking time of S2 is 23-25 h, for example, 23.5 h, 24h, and 24.5 h. And after the large material is placed in a lower piece, the large material is subjected to heat refining, so that the materials are added and mixed conveniently. When the large materials and the accelerator are mixed and uniformly dispersed to obtain the mixed rubber, the mixed rubber is refined, the dispersion uniformity between the rubber and the compounding agent is increased, and the performance effect of the material is improved.
In this embodiment, in S1 and S2, an internal rubber mixer may be used to respectively heat or plasticate the epdm rubber; the main material is mixed and uniformly dispersed. In S3, an open type rubber mixing mill can be adopted to mix the big materials, namely, the big materials are uniformly dispersed; after the rubber compound is obtained, the rubber compound can be refined by an open rubber mixing mill.
In the second exemplary embodiment of the present invention, the sealing rubber may include the sealing rubber prepared by the preparation method described in the above first exemplary embodiment. Through tests, the hardness of the sealing rubber is 55-60, the strength is not less than 12, and the elongation is not less than 500. In the third exemplary embodiment of the present invention, the sealing capsule may be made of the sealing rubber prepared by the preparation method described in the above-described first exemplary embodiment. Here, the primary side water chamber of the evaporator is an important operation for the overhaul of the nuclear power plant, and has a large radiation risk and severe working conditions, and no matter in any sealing structure mode, the sealing capsule is required to have the characteristics of high radiation resistance, lighter weight, long service life and the like. The formula of the invention has multiple environmental media and use requirements of radiation aging resistance, acid resistance, small specific gravity, tear resistance, durability of anti-explosion capability and the like, and is designed to be more than or equal to 30mSv/h at the irradiation level and have the service life of not less than 1080 h.
In summary, the beneficial effects of the invention can include at least one of the following:
(1) the invention has the characteristics of higher radiation resistance, lighter weight, long service life and the like, and has the advantages of high rebound resilience, air inflation, stability, durability, easy installation and the like;
(2) the invention can be directly applied to the third generation nuclear power project in China, and the related test condition can also provide reference for the design and improvement of the steam generator blocking plate of other nuclear power stations, thereby having higher economic value.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of sealing rubber is characterized by comprising the following steps:
plasticating or hot-smelting 80-120 parts of ethylene propylene diene monomer rubber by mass to obtain a main body material;
mixing the main body material with 10-30 parts of an active agent, 30-60 parts of a reinforcing agent, 30-60 parts of a softening agent and 30-90 parts of a radiation-resistant filler for one time, and uniformly dispersing to obtain a large material;
and after the large material is placed, mixing the large material with 3-15 parts of accelerator and 0.5-2 parts of vulcanizing agent for the second time, and dispersing uniformly to obtain the sealing rubber.
2. The method for producing a sealing rubber according to claim 1, further comprising:
before the secondary mixing, the large materials are subjected to heat refining so as to be beneficial to adding materials;
and refining the sealing rubber after secondary mixing to improve the dispersion uniformity of each component and the main material.
3. The method for producing a sealing rubber according to claim 1, wherein the active agent comprises: zinc oxide, stearic acid and a silane coupling agent;
wherein, in the activating agent, the mass ratio of zinc oxide is 30-50%, the mass ratio of stearic acid is 3-10%, and the mass ratio of silane coupling agent is 30-50%.
4. The method for producing a sealing rubber according to claim 1, wherein the reinforcing agent is highly abrasion-resistant carbon black, the softening agent is paraffin oil, and the vulcanizing agent is sulfur.
5. The method for producing a sealing rubber according to claim 1, wherein the radiation-resistant filler comprises: bismuth trioxide, nano barite and rare earth gadolinium oxide;
wherein, in the anti-radiation filler, the mass ratio of the bismuth trioxide is 20-50%, the mass ratio of the nano barite is 20-50%, and the mass ratio of the rare earth gadolinium oxide is 20-50%.
6. The method for producing a sealing rubber according to claim 1, wherein the accelerator includes: TBZTD, CZ, DM, DTDC and BZ;
wherein in the accelerant, the mass ratio of TBZTD is 20-35%, the mass ratio of CZ is 20-35%, the mass ratio of DM is 10-20%, the mass ratio of DTDC is 10-20%, and the mass ratio of BZ is 10-20%.
7. The method for preparing a sealing rubber according to claim 1, wherein the temperature of the plastication or the heat mastication is 120 to 140 ℃, the time is 3 to 5min, and the pressure is 0.3 to 1.0 Mpa.
8. The method for producing a sealing rubber according to claim 1, wherein the temperature of the primary kneading and the secondary kneading is 130 to 150 ℃, the time is 8 to 25min, and the pressure is 0.3 to 1.0 Mpa.
9. A sealing rubber, characterized in that the sealing rubber comprises the sealing rubber prepared by the preparation method of any one of claims 1 to 8.
10. A sealed capsule characterized in that it is made of the sealing rubber according to claim 9.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210286525.0A CN114591573A (en) | 2022-03-23 | 2022-03-23 | Sealing rubber, preparation method thereof and sealing capsule |
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| CN202210286525.0A CN114591573A (en) | 2022-03-23 | 2022-03-23 | Sealing rubber, preparation method thereof and sealing capsule |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722471A (en) * | 2017-10-23 | 2018-02-23 | 陕西特种橡胶制品有限公司 | Nuclear steam generator closure plate air bag resistance to irradiation rubber and preparation method thereof |
| CN112225956A (en) * | 2020-10-15 | 2021-01-15 | 杨杨 | Radiation-proof composite material, preparation method and application thereof |
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2022
- 2022-03-23 CN CN202210286525.0A patent/CN114591573A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722471A (en) * | 2017-10-23 | 2018-02-23 | 陕西特种橡胶制品有限公司 | Nuclear steam generator closure plate air bag resistance to irradiation rubber and preparation method thereof |
| CN112225956A (en) * | 2020-10-15 | 2021-01-15 | 杨杨 | Radiation-proof composite material, preparation method and application thereof |
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