CN115651363A - Epoxy resin-based shielding material and preparation method thereof - Google Patents
Epoxy resin-based shielding material and preparation method thereof Download PDFInfo
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- CN115651363A CN115651363A CN202211396163.7A CN202211396163A CN115651363A CN 115651363 A CN115651363 A CN 115651363A CN 202211396163 A CN202211396163 A CN 202211396163A CN 115651363 A CN115651363 A CN 115651363A
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Abstract
The invention provides an epoxy resin-based shielding material and a preparation method thereof, and relates to the field of radiation-proof materials. The epoxy resin-based shielding material comprises the following raw materials: 29-39 parts of glycidyl amine type epoxy resin, 6-8 parts of novolac epoxy resin, 32-42 parts of aromatic amine curing agent, 5-8 parts of radiation shielding material and 15-27 parts of processing aid. 6. The epoxy resin-based shielding material provided by the invention has the advantages of high temperature resistance, heat insulation and light weight, is suitable for high-radioactivity, high-temperature and high-humidity environments, can resist high temperature of more than 190 ℃ under a medium-break water loss accident, can effectively block heat and reduce heat conduction, has a relative change rate of bending strength of less than 5% after damp-heat aging, can ensure the integrity of a typical shielding structure and the effectiveness of shielding protection on the premise that the total weight is increased by not more than 4%, and is a good radiation shielding material for a nuclear reactor island area of a nuclear power station.
Description
Technical Field
The invention relates to the field of radiation-proof materials, in particular to an epoxy resin-based shielding material and a preparation method thereof.
Background
Nuclear energy has the characteristics of energy conservation, high efficiency, environmental protection and the like, and has become a necessary choice for coping with energy crisis and environmental stress in various countries in the world. However, the nuclear reaction, while releasing energy, is inevitably accompanied by nuclear radiation that is extremely harmful to the human body, environment, and equipment. Therefore, the use of nuclear energy must be based on safety. Nuclear radiation includes various charged or uncharged particles and rays, such as neutrons, gamma rays, and the like.
Usually, nuclear power facilities adopt polyethylene-based shielding materials, which have the advantages of high shielding effect, light weight and the like, but one remarkable defect is that the heat distortion temperature is low, and the normal use temperature is below 90 ℃. Generally, the polyethylene-based shielding material cannot work normally at an ambient temperature of more than 90 ℃, which limits the application of the polyethylene-based shielding material in a higher temperature environment, and particularly when a loss of coolant accident (LOCA) occurs, the higher temperature (about 190 ℃) can cause softening, deformation and the like of the shielding material, so that the shielding effect of the shielding material is reduced and even fails, thereby generating a radiation safety hazard.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the polyethylene-based shielding material in the prior art is easy to soften and deform under the high-radioactivity, high-temperature and high-humidity environment to cause potential safety hazard, thereby providing the epoxy resin-based shielding material and the preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
in a first aspect, the invention provides an epoxy resin-based shielding material, which comprises the following raw materials in parts by weight:
29 to 39 parts of glycidyl amine type epoxy resin,
6 to 8 parts of phenolic epoxy resin,
32 to 42 portions of aromatic amine curing agent,
5 to 8 parts of radiation shielding material,
15-27 parts of a processing aid.
Further, the glycidyl amine type epoxy resin has an epoxy equivalent of 110 to 130g/eq and a viscosity of 3000 to 8000mPa.s at 50 ℃; the epoxy equivalent of the novolac epoxy resin is 185-195 g/eq.
Further, the aromatic amine-based curing agent includes diaminodiphenyl sulfone and diethyltoluene diamine, and the active hydrogen equivalent ratio of diaminodiphenyl sulfone to diethyltoluene diamine is 3:7.
furthermore, the water solubility of the diamino diphenyl sulfone at 20 ℃ is less than 0.1g/100mL, and the particle size is 60-80 μm; the purity of the diethyltoluenediamine is more than or equal to 98 percent.
Further, the radiation shielding material comprises boron carbide powder, wherein the total boron content of the boron carbide powder is more than or equal to 76%, and the particle size is 60-80 μm.
Further, the processing aid comprises at least one of a toughening agent, a defoaming agent, a wetting dispersant and a thixotropic agent.
Further, the processing aid comprises the following components in parts by weight:
10-15 parts of a toughening agent,
0.08 to 0.1 portion of defoaming agent,
1-3 parts of a wetting dispersant,
0.3 to 1.5 portions of thixotropic agent.
Further, the toughening agent is epoxy resin with a core-shell rubber structure, the rubber content of the epoxy resin is 40%, the epoxy equivalent is 300g/eq, and the viscosity at 50 ℃ is 25000mPa.s.
Further, the defoaming agent is an organic silicon defoaming agent, and the density is 0.99g/mL.
Further, the thixotropic agent is an organically modified magnesium aluminum silicate compound with densityIs 1.5 to 1.7g/cm 3 。
In a second aspect, the invention provides a method for preparing the epoxy resin-based shielding material, which comprises the following steps:
(1) Uniformly mixing the raw material components to form a castable;
(2) Pouring the casting material after vacuum defoaming, and forming a semi-finished product through high-temperature curing;
(3) And machining the semi-finished product to obtain the epoxy resin-based shielding material.
Further, the high-temperature curing process comprises the following steps: heating at 110 deg.C for 1h, at 120 deg.C for 1h, at 160 deg.C for 2h, and at 200 deg.C for 2h.
Further, in the step (1), dissolving diamino diphenyl sulfone in a solvent to obtain a diamino diphenyl sulfone solution, uniformly mixing glycidyl amine type epoxy resin, novolac epoxy resin and the diamino diphenyl sulfone solution, and removing the solvent in vacuum to form a mixture 1;
uniformly mixing the mixture 1 with a toughening agent, a defoaming agent and diethyltoluenediamine to form a mixture 2;
uniformly mixing the mixture 2 with a radiation shielding material to form a mixture 3;
and uniformly mixing the mixture 3 with a wetting dispersant and a thixotropic agent to form the castable.
Further, the density of the epoxy resin-based shielding material is 1.25 +/-0.1 g/cm 3 。
The technical scheme of the invention has the following advantages:
1. the epoxy resin-based shielding material provided by the invention comprises the following raw materials: glycidyl amine type epoxy resin, novolac epoxy resin, aromatic amine curing agent, radiation shielding material and processing aid. In order to improve the heat resistance of the shielding material, glycidol amine type epoxy resin with three functionality degrees and a benzene ring in the structure is selected as main matrix resin, the resin has the advantages of high activity, low viscosity, chemical medium resistance and the like, but due to the existence of a large amount of amino groups, the resin has strong hygroscopicity, and the environment moisture and heat resistance after curing and forming is not stable enough, so that phenolic epoxy resin without hydrophilic groups in the molecular structure and good water resistance is selected as secondary matrix resin, and the compatibility of the two can make up for the deficiency. Although the addition of the novolac epoxy resin can obviously improve the humidity resistance and the heat resistance of the material, the heat resistance of the shielding material is reduced along with the increase of the content of the novolac epoxy resin, and the content of the novolac epoxy resin in the matrix resin (preferably 10-20%) is determined by comprehensively considering the heat deformation temperature and the humidity resistance of the material. The heat resistance of the material can be improved by introducing a heat-resistant group and a rigid structure into the system. The molecular structure of the aromatic amine curing agent contains a stable benzene ring structure, and the aromatic amine curing agent and the cured epoxy resin have good heat resistance.
2. The epoxy resin-based shielding material provided by the invention preferably uses diaminodiphenyl sulfone and diethyltoluenediamine as compound curing agents. And the diamino diphenyl sulfone is solid and can obviously increase the viscosity of the system after being mixed with the epoxy resin, and in order to ensure that the epoxy casting material can be operated well, liquid diethyl toluene diamine is selected as a curing agent to adjust the viscosity of the system. Through test, when the equivalent ratio of active hydrogen is 3:7, the physical and mechanical properties, heat resistance and technological properties of the material are better.
3. According to the epoxy resin-based shielding material provided by the invention, as the epoxy resin with high functionality and rigid groups and the aromatic amine curing agent are adopted, the crosslinking density of the material is high, and the toughness after curing is poor, so that the toughening agent is preferably added to toughen and modify the system. The toughening agent with the core-shell rubber structure can be used as a second phase to improve the toughness without influencing the thermal deformation temperature of the shielding material, and the effect that the addition amount does not exceed 30 percent of that of the epoxy resin is the best through experimental verification.
4. According to the epoxy resin-based shielding material provided by the invention, high-purity nuclear-grade boron carbide is preferably selected as the shielding material, the total boron content is more than or equal to 76%, and through heat transfer analysis and Monte Carlo simulation calculation, when the content is within the range of 5-8%, the optimal neutron shielding effect can be achieved, and the heat conductivity coefficient of the composite shielding material cannot be obviously improved.
5. The epoxy resin-based shielding material provided by the invention further determines the optimal matrix resin proportion, curing process and parameters by means of test comparison, an epitaxial method and the like, so that the temperature resistance of the epoxy resin-based shielding material is higher than 200 ℃, and the quality of a molded sample is stable and reliable.
6. The epoxy resin-based shielding material provided by the invention has the advantages of high temperature resistance, heat insulation and light weight, is suitable for high-radioactivity, high-temperature and high-humidity environments, can resist high temperature of more than 190 ℃ under a medium-break water loss accident, can effectively block heat and reduce heat conduction, has a relative change rate of bending strength of less than 5% after damp-heat aging, can ensure the integrity of a typical shielding structure and the effectiveness of shielding protection on the premise that the total weight is increased by not more than 4%, and is a good radiation shielding material for a nuclear reactor island area of a nuclear power station. The results of application and verification on some onshore nuclear power facility prove that the integrity and the effectiveness of the whole shielding structure can be effectively ensured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an epoxy-based shielding material developed;
FIG. 2 is a comparison graph of the pre-and post-test effects of the test groups in the crevasse loss of coolant accident simulation test;
fig. 3 is a comparison graph of the pre-and post-test effect of the control group in the crevasse loss of coolant accident simulation test.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
In the examples, the sources of the raw materials are as follows:
glycidyl amine type epoxy resin (liquid), ML-3102L, epoxy equivalent of 110-130 g/eq, viscosity of 3000-8000mPa.s (50 ℃);
novolac epoxy resin (liquid), F-51, epoxy equivalent 185-195 g/eq;
diamino diphenyl sulfone (solid), DDS, water solubility <0.1g/100ml (20 ℃), particle size less than 250 μm;
diethyl toluenediamine (liquid), E-100, with a purity of more than or equal to 98%;
boron carbide (powder), F220, the total content of boron is more than or equal to 76 percent, and the grain diameter is 60-80 mu m;
toughening agent (liquid), MX-154, epoxy resin with core-shell rubber structure, 40% of rubber content, about 300g/eq of epoxy equivalent, and about 25000mPa.s (50 ℃) of viscosity;
defoaming agent (liquid), BYK-1799, organosilicon defoaming agent, have stronger defoaming ability, the density is about 0.99g/mL;
the wetting dispersant (yellow transparent liquid), HX4010, has excellent wetting dispersing and viscosity reducing effects, and improves the leveling property of the product;
thixotropic agent (grey white powder), GARAMIDE-1958, organic modified magnesium aluminum silicate compound, density 1.5-1.7 g/cm 3 It enables systems with excellent anti-settling and anti-sag properties, whether at high or low viscosity.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The raw materials or equipment used are all conventional products commercially available, including but not limited to those used in the examples of the present application.
Example 1
An epoxy resin-based shielding material comprises the following raw materials:
the preparation method of the epoxy resin-based shielding material comprises the following steps:
(1) Pouring glycidyl amine type epoxy resin, novolac epoxy resin and diaminodiphenyl sulfone (the concentration is 30 g/mL) dissolved in acetone into an electric stirrer, fully mixing at the temperature of 50-60 ℃ and the rotating speed of not less than 900r/min for 40min, and removing an acetone solvent in vacuum to form a mixture 1;
(2) Pouring the toughening agent, the defoaming agent and the diethyltoluenediamine into the mixture 1, and fully mixing the mixture for 40min at a rotation speed of not less than 900r/min in an electric mixer at a temperature of between 50 and 60 ℃ to form a mixture 2;
(3) Pouring boron carbide into the mixture 2, and fully mixing the mixture for 50 to 50 minutes at a rotating speed of not less than 900r/min in an electric mixer at a temperature of between 50 and 60 ℃ to form a mixture 3;
(4) Pouring the wetting dispersant and the thixotropic agent into the mixture 3, and fully mixing the mixture for 30min at a rotating speed of not less than 900r/min in an electric mixer at a temperature of between 50 and 60 ℃ to form a castable;
(5) Pouring the casting material into a die preheated at 100 ℃, and heating and curing in an oven, wherein the specific process comprises the following steps: heating at 110 ℃ for 1h → heating at 120 ℃ for 1h → heating at 160 ℃ for 2h → heating at 200 ℃ for 2h, and then naturally cooling to room temperature to form a semi-finished product;
(6) And (3) pressing and standing the semi-finished product for 1 day, cutting and polishing the semi-finished product into a plate with the thickness of 40cm multiplied by 40cm and the thickness of 3 cm. As shown in fig. 1.
Example 2
An epoxy resin-based shielding material comprises the following raw materials:
the preparation method is the same as example 1.
Examples of the experiments
The epoxy resin-based shielding materials prepared in examples 1 and 2 were subjected to performance tests, and the test items, test results, and test methods are shown in table 1.
TABLE 1 Performance test results for epoxy resin-based shielding materials
The test results in table 1 show that the epoxy resin-based shielding material provided by the invention has excellent properties.
In order to further verify the practical application effect of the epoxy resin-based shielding material provided by the invention, a breach water loss accident simulation test is carried out according to the following method:
experimental groups: lead plate (60 cm. Times.60 cm, thickness 3.5 cm) + epoxy-based shielding material prepared in example 1 (60 cm. Times.60 cm, thickness 3 cm) + boron-containing polyethylene plate (60 cm. Times.60 cm, thickness 7 cm);
control group: lead plate (60 cm × 60cm, thickness 3.5 cm) + boron-containing polyethylene plate (60 cm × 60cm, thickness 7 cm).
The experimental procedures and conditions are as follows: heating according to the LOCA accident time-temperature curve, and keeping at 190 deg.C for 2h. After the test was completed, the appearance, size and weight of the shielding material involved in the test were checked.
The results of the experiment are shown in FIGS. 2 to 3. When the epoxy resin-based shielding plate is not used in the control group, the boron-containing polyethylene plate is seriously deformed, the maximum unidirectional shrinkage is about 14.5mm, and the deformation of the plate causes serious ray penetration gaps to be formed around the boron-containing polyethylene plate. The results of the experimental group show that the epoxy resin-based shielding plate prepared in the embodiment 1 has no deformation and good heat resistance, the deformation of the subsequent boron-containing polyethylene plate is obviously reduced compared with that of a control group, the maximum unidirectional size is shrunk within 1.5mm, and the radiation safety of personnel can be guaranteed.
Therefore, the epoxy resin-based shielding plate provided by the invention can keep the integrity and effectiveness of a shielding structure under the high-temperature environment condition of 190 ℃ in a breach water loss accident, and the epoxy resin-based shielding plate with the thickness of 3cm can reduce the high temperature of 190 ℃ to below 90 ℃, so that the normal use of non-high-temperature-resistant shielding materials such as follow-up polyethylene and the like can be guaranteed.
The materials prepared in the embodiment 1 and the embodiment 2 are applied to a certain pressurized water reactor test device project, and the epoxy resin-based shielding material provided by the invention can completely meet the requirements of reactor operation and engineering application.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The epoxy resin-based shielding material is characterized by comprising the following raw materials in parts by weight:
29 to 39 portions of glycidylamine type epoxy resin,
6 to 8 parts of phenolic epoxy resin,
32 to 42 portions of aromatic amine curing agent,
5 to 8 parts of radiation shielding material,
15-27 parts of a processing aid.
2. The epoxy-based shielding material according to claim 1, wherein the glycidyl amine type epoxy resin has an epoxy equivalent of 110 to 130g/eq and a viscosity of 3000 to 8000mpa.s at 50 ℃; the epoxy equivalent of the novolac epoxy resin is 185-195 g/eq.
3. The epoxy-based shielding material according to claim 1, wherein the aromatic amine-based curing agent comprises diaminodiphenyl sulfone and diethyltoluene diamine, and the active hydrogen equivalent ratio of diaminodiphenyl sulfone to diethyltoluene diamine is 3:7.
4. The epoxy resin-based shielding material of claim 1, wherein the radiation shielding material comprises boron carbide powder, the boron carbide powder has a total boron content of at least 76% and a particle size of 60-80 μm.
5. The epoxy resin-based shielding material according to claim 1, wherein the processing aid comprises at least one of a toughening agent, a defoaming agent, a wetting dispersant, a thixotropic agent.
6. The epoxy resin-based shielding material as claimed in claim 5, wherein the processing aid comprises, in parts by weight:
10-15 parts of a toughening agent,
0.08 to 0.1 portion of defoaming agent,
1 to 3 parts of wetting dispersant,
0.3 to 1.5 portions of thixotropic agent.
7. The epoxy-based shielding material according to claim 5,
the toughening agent is epoxy resin with a core-shell rubber structure, the rubber content of the toughening agent is 40%, the epoxy equivalent is 300g/eq, and the viscosity is 25000mPa.s at 50 ℃;
the defoaming agent is an organic silicon defoaming agent, and the density is 0.99g/mL;
the thixotropic agent is an organically modified aluminum magnesium silicate compound with the density of 1.5-1.7 g/cm 3 。
8. The method for preparing an epoxy resin-based shielding material according to any one of claims 1 to 7, comprising the steps of:
(1) Uniformly mixing the raw material components to form a castable;
(2) Pouring the casting material after vacuum defoaming, and forming a semi-finished product through high-temperature curing;
(3) And machining the semi-finished product to obtain the epoxy resin-based shielding material.
9. The method for preparing the epoxy resin-based shielding material according to claim 8, wherein the high-temperature curing process comprises: heating at 110 deg.C for 1h, at 120 deg.C for 1h, at 160 deg.C for 2h, and at 200 deg.C for 2h.
10. The method for preparing the epoxy resin-based shielding material according to claim 8, wherein in the step (1), diaminodiphenyl sulfone is dissolved in a solvent to obtain a diaminodiphenyl sulfone solution, glycidyl amine type epoxy resin, novolac epoxy resin and diaminodiphenyl sulfone solution are uniformly mixed, and the solvent is removed in vacuum to form a mixture 1;
uniformly mixing the mixture 1 with a toughening agent, a defoaming agent and diethyltoluenediamine to form a mixture 2;
uniformly mixing the mixture 2 with a radiation shielding material to form a mixture 3;
and uniformly mixing the mixture 3 with a wetting dispersant and a thixotropic agent to form the castable.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211396163.7A CN115651363A (en) | 2022-11-07 | 2022-11-07 | Epoxy resin-based shielding material and preparation method thereof |
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| CN202211396163.7A CN115651363A (en) | 2022-11-07 | 2022-11-07 | Epoxy resin-based shielding material and preparation method thereof |
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