KR102122993B1 - Neutron shielding material and manufacturing method thereof - Google Patents

Abstract

One embodiment of the present invention is an epoxy resin 20 to 30 parts by weight; 10-20 parts by weight of an amine-based curing agent; 50 to 65 parts by weight of aluminum hydroxide and zinc borate surface-treated with a titanium- or silicon-based surface treatment agent; 1 to 7 parts by weight of boron carbide surface-treated with a polyolefin-based resin; And borated graphene and a density increasing agent 0.1 to 15 parts by weight; provides a neutron shielding composition using a boron-doped graphene and a method of manufacturing the same.

Description

Composition of neutron shielding material using boron-doped graphene and its manufacturing method{NEUTRON SHIELDING MATERIAL AND MANUFACTURING METHOD THEREOF}

The present invention relates to a composition having improved neutron shielding performance using graphene and a method of manufacturing the same, and more particularly, to an neutron shielding material composition having an improved neutron shielding performance and excellent heat resistance and thermal conductivity, and a method for manufacturing the same.

Neutrons are generated from the transport and storage of radioactive materials, nuclear fuel reprocessing plants, nuclear reactors, liquid metal furnaces, medical equipment or devices, etc., which have high energy, high permeability, and (n, γ) secondary gamma rays by reaction. Since it occurs and impairs the human body, there is a need for a neutron shielding material composition capable of safely shielding neutrons.

It is known that neutrons are absorbed by boron, but in order for boron to absorb neutrons, it is necessary to slow down the neutrons. Hydrogen is known as an optimal material for decelerating neutrons, and hydrogen atoms collide with high-speed neutrons in neutrons to absorb energy, thereby effectively decelerating neutrons. Therefore, the more the neutron shielding material composition contains hydrogen and boron, the more effective the neutron shielding may be.

For this reason, it has been proposed to use water, which is a material having a high hydrogen density, as a material for the shielding material composition, but it is difficult to handle because it is a liquid. In particular, it is not suitable for casks for transportation and storage purposes, and is 100°C. There is a problem that it is difficult to suppress boiling in the cask reaching the above.

In addition, since decay heat is generated when neutrons are generated, heat is generated when the cask is sealed, and the inside becomes high temperature. Therefore, the cask has several fins designed to escape heat in preparation for volume expansion due to temperature rise, but requires extra space, and this extra space must be made into a complex structure in consideration of the neutron shielding effect. Due to this, the thickness and weight of the cask increases and the capacity (payload) of the cask decreases.

Therefore, in order to secure the capacity of the cask, the cask must be expanded. However, when the cask is expanded, it is difficult to implement the thermal conductivity, heat resistance, and neutron absorption performance of the neutron shielding material, so research and development are needed to solve these problems.

The present invention is to solve the problems of the prior art described above, the object of the present invention is to improve the low-speed neutron absorption capacity by doping boron atoms in graphene, excellent thermal conductivity, heat resistance, and a neutron shielding material that can effectively absorb neutrons It is to provide a composition and its manufacturing method.

In order to achieve the above object, the present invention is an epoxy resin 20 to 30 parts by weight; 10-20 parts by weight of an amine-based curing agent; 50 to 65 parts by weight of aluminum hydroxide and zinc borate surface-treated with a titanium- or silicon-based surface treatment agent; 1-7 parts by weight of boron carbide surface-treated with a polyolefin-based resin; And 0.1 to 15 parts by weight of borated graphene and a density increasing agent; and the density increasing agent is a metal powder, a metal oxide powder, or a mixture thereof, and the borated graphene and the density increasing agent are 20 to 20, respectively. 80: It is mixed in a weight ratio of 80 to 20.

The epoxy resin is characterized in that a mixture of bisphenol A type epoxy resin and hydrogenated epoxy resin, alkyl glycidyl ether (Clycyl ether) (Glycidal ether).

It characterized in that the amine-based curing agent is one selected from the group consisting of polyamidoamine, polyetherdiamine, polyoxypropylenediamine, triethylene tetraamine, and reactants reacting these curing agents with tall oil fatty acids, and a mixture of two or more of these. .

It characterized in that the average particle size of the aluminum hydroxide surface-treated with the titanium-based surface treatment agent is 1.0㎛ to 40㎛.

It characterized in that the average particle size of the aluminum hydroxide surface-treated with the silicon-based surface treatment agent is 15㎛ to 30㎛.

It is characterized in that the polyolefin-based resin is polypropylene.

The density increasing agent is characterized in that the metal powder, metal oxide powder, or a mixture thereof.

According to another feature of the present invention, the present invention is prepared by mixing (a) 20 to 30 parts by weight of an epoxy resin, and 50 to 65 parts by weight of aluminum hydroxide and zinc borate surface-treated with a titanium- or silicon-based surface treatment agent. To do; (b) 10 to 20 parts by weight of the amine curing agent, 1 to 7 parts by weight of boron carbide surface-treated with a polyolefin resin to prepare a second mixture; (c) preparing a third mixture by mixing borated graphene with 0.1-15 parts by weight of a density increasing agent, and 1-10 parts by weight of a dispersing agent; (d) preparing a fourth mixture by mixing 50-60% by weight of the third mixture with the first mixture; (e) mixing the remaining amount of the third mixture and the second mixture to prepare a fifth mixture; (f) mixing the fourth and fifth mixtures. .

The temperature in step (a) is adjusted to 35°C to 45°C.

The temperature in step (b) is adjusted to 20°C to 30°C.

The neutron shielding material composition according to an aspect of the present invention, borated graphene, wax epoxy resin, amine-based curing agent, titanium hydroxide surface treatment with aluminum hydroxide and zinc borate 50-65 nano boron carbide, and nano tungsten density increase In addition to maximizing thermal conductivity, heat resistance, and neutron absorption ability within a limited shielding area including agents, there is an effect of shielding gamma rays.

In addition, the improved thermal conductivity and heat resistance can improve the heat dissipation, which is a problem of known casks, to reduce the number of heat dissipation fins, and it is possible to expand the storage system of nuclear fuel after use. Can be.

It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a conceptual diagram schematically showing a method of manufacturing a neutron shielding material composition according to an embodiment of the present invention.
FIG. 2 is a flowchart sequentially showing a method of manufacturing the neutron shielding material composition shown in FIG. 1.
Figure 3 is a TGA (Thermogravimetric analysis, thermal weight analysis) graph of aluminum hydroxide surface-treated with a silicon-based surface treatment agent according to an embodiment of the present invention
Figure 4 is a SEM image of B4C constituting an embodiment of the present invention.
5 is an image of a borated graphene SEM constituting an embodiment of the present invention.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. It should be noted that in adding reference numerals to the components of each drawing, the same components have the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the embodiments of the present invention, when it is determined that detailed descriptions of related well-known structures or functions interfere with the understanding of the embodiments of the present invention, detailed descriptions thereof will be omitted.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. It should be noted that in adding reference numerals to the components of each drawing, the same components have the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the embodiments of the present invention, when it is determined that detailed descriptions of related well-known structures or functions interfere with the understanding of the embodiments of the present invention, detailed descriptions thereof will be omitted.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

(Neutron shielding material composition)

One aspect of the present invention is an epoxy resin 20 to 30 parts by weight; 10-20 parts by weight of an amine-based curing agent; 50 to 65 parts by weight of aluminum hydroxide and zinc borate surface-treated with a titanium- or silicon-based surface treatment agent; 1 to 7 parts by weight of boron carbide surface-treated with a polyolefin-based resin; And 0.1 to 15 parts by weight of borated graphene and a density increasing agent.

The neutron shielding material composition may be prepared based on a polymer, and an epoxy resin having excellent heat resistance may be used as the polymer subject. In addition, the epoxy resin is generally used in the form of a liquid, when mixed with a curing agent has the advantage of excellent moldability at room temperature.

As the epoxy resin, various types of a mixture of glycidyl ether or glycidyl amine type of alkyl C10-C15 may be used, such as bisphenol A type, bisphenol brominated, bisphenol F type, phenol noblock type, and the like. In comparison, glycidyl ether and glycidyl are contained in a bisphenol A-type epoxy resin having superior shielding stability by containing a relatively large amount of hydrogen atoms compared to other epoxy resins, and neutrons collide with the hydrogen atoms to lose a lot of energy. Dill amines can be used mixed.

The bisphenol A-type epoxy resin may be used in a liquid prepolymer by mixing it with Aliphatic glycidyl ether, Butyl glycidyl ether, or mixtures thereof. By mixing and using these, excellent workability can be obtained compared with the case where bisphenol A type epoxy resin is used alone.

In addition, the content of the epoxy resin in the neutron shielding material composition may be 20 to 30 parts by weight. When the content of the epoxy resin is less than 20 parts by weight, the viscosity of the neutron shielding material composition rises, and excessive mixing may result in deterioration of homogeneity and moldability. If it exceeds 30 parts by weight, ?t of other materials is relatively As it is written, the required level of flame retardancy and mechanical strength cannot be achieved.

Meanwhile, the neutron shielding material composition may include a curing agent that reacts with an epoxy resin to form a crosslinked structure, and the curing agent may be an amine-based curing agent. The curing agent is used to cure the liquid epoxy resin, and the amine-based curing agent also has a high hydrogen content, so that the neutron shielding performance can be further enhanced.

The amine-based curing agent may be one selected from the group consisting of polyamidoamine, polyetherdiamine, polyoxypropylenediamine, and triethylene tetraamine, and reactants reacting these curing agents with tall oil fatty acids, and a mixture of two or more of them, The amine-based curing agent may be prepared by dehydrating a fatty acid (Fatty acid), tetraethylene pentamine (Tetraethyene pentamine), or a mixture thereof.

The content of the amine-based curing agent may be 10 to 20 parts by weight, and if it is less than 10 parts by weight, the curing effect may be weak, and when it exceeds 20 parts by weight, the curing speed is excessively fast, and sufficient working time cannot be secured.

The neutron shielding material composition may include a flame retardant. The flame retardant may be aluminum hydroxide, preferably, aluminum hydroxide surface-treated with a titanium-based or silicon-based surface treatment agent.

The flame retardant has an organic flame retardant and an inorganic flame retardant, and unlike the organic flame retardant, the inorganic flame retardant is not volatilized by heat and decomposes to release non-combustible gases such as H 2 O, CO 2, SO 2 and HCl, and most endothermic reactions occur.

In addition, in the gas phase, there is an effect of diluting the combustible gas, preventing the access of oxygen by applying the plastic surface, and at the same time, reducing the production of plastic cooling and pyrolysis products through an endothermic reaction on the solid phase surface.

Among the inorganic flame retardants, aluminum hydroxide is widely used because it is inexpensive and can be easily put into plastics. The aluminum hydroxide is a crystalline water-type compound containing 35% water, and in case of fire, no toxic gas is generated and self-extinguishing.

On the other hand, since the thermal decomposition temperature of the aluminum hydroxide is about 200°C, there is a disadvantage that it can be used only for plastics having a low processing temperature. Therefore, the aluminum hydroxide can be used by surface treatment with a titanium-based or silicon-based surface treatment agent.

The aluminum hydroxide surface-treated with the titanium-based or silicon-based surface treatment agent may have excellent dispersibility and kneading properties, thereby lowering the viscosity of the epoxy resin, and accordingly, workability may be improved when manufacturing the neutron shielding material composition.

For example, the titanium- and silicon-based surface treatment agent may be a metal or a non-metal itself or an oxide thereof, preferably titanium dioxide (TiO2) and silicon dioxide (SiO2), respectively, but is not limited thereto. When the aluminum hydroxide, specifically, the aluminum hydroxide on the powder is surface-treated using an oxide-type surface treatment agent, an oxide layer may be formed on the surface of the powder.

In addition, ?t amount of the titanium- or silicon-based surface-treated aluminum hydroxide may be 50 to 65 parts by weight. If the content of the surface-treated aluminum hydroxide is less than 50 parts by weight, heat resistance may be deteriorated, and if it is more than 65 parts by weight, excellent heat resistance may be secured, but neutron shielding performance may be deteriorated due to relatively low content of other materials. have.

In general, the aluminum hydroxide is preferably used in a powder form, the average particle size of the aluminum hydroxide surface-treated with the titanium-based surface treatment agent may be 1.0㎛ to 40㎛. If the average particle size of the aluminum hydroxide surface-treated with the titanium-based surface treatment agent is less than 1.0 µm, viscosity may increase, so that kneading may take a lot of time, and if it exceeds 40 µm, the surface area of the aluminum hydroxide may be reduced and heat resistance may deteriorate. .

In addition, the average particle size of the aluminum hydroxide surface-treated with the silicon-based surface treatment agent may be 15 μm to 30 μm. If the average particle size of the aluminum hydroxide surface-treated with the silicon-based surface treatment agent is less than 15 μm, viscosity may increase, which may take a lot of time for kneading, and if it exceeds 30 μm, the surface area of the aluminum hydroxide may be small and heat resistance may deteriorate.

3 is a TGA (Thermogravimetric analysis) graph of aluminum hydroxide surface-treated with a silicon-based surface treatment agent according to an embodiment of the present invention. Referring to FIG. 2, it can be seen that aluminum hydroxide surface-treated with a silicon-based surface treatment agent indicated by a solid black line has a higher thermal decomposition temperature than aluminum hydroxide not treated with other surfaces. Specifically, the thermal decomposition behavior of the surface treated and untreated aluminum hydroxide starts at a similar temperature, but the gap widens as the thermal decomposition progresses. For example, when comparing the temperature at which a weight loss of about 10% occurs, the surface-treated aluminum hydroxide is about 340°C, while the other untreated aluminum hydroxide is about 310 to 320°C, showing a significant difference. Therefore, it can be confirmed that the heat resistance of the surface-treated aluminum hydroxide was excellent.

The neutron shielding material composition is a neutron absorber, and may be prepared by including boron carbide surface-treated with a polyolefin-based resin.

A boron compound may be used as the neutron absorber, and the boron compound is from a group consisting of boron carbide, boron nitride, boric anhydride, iron boron, calcite, orthoboric acid, metaboric acid, zinc borate, and mixtures of two or more of them. It may be the one chosen.

In particular, boron carbide has a high content of neutron trapping neutrons, so it has excellent neutron shielding performance to absorb low-speed neutrons or thermal neutrons, and when the boron carbide is irradiated with neutrons, it generates high-level secondary radiation or secondary by-products. Do not order.

4 is an SEM image of boron carbide (B4C) surface-treated with a polyolefin-based resin according to an embodiment of the present invention.

Referring to FIG. 4, the boron carbide may be surface treated with a polyolefin-based resin that is a hydrocarbon-based material containing a large amount of hydrogen atoms. The polyolefin-based resin is used to increase the hydrogen content in the neutron shielding material composition, and preferably, the polyolefin-based resin may be a polypropylene resin.

The average particle size of the polypropylene resin may be 70㎛ to 160㎛. If the average particle size of the polypropylene resin is less than 70 μm, the viscosity may rise excessively, and kneading may be difficult. If it is more than 160 μm, the volume of the polypropylene resin may increase, resulting in poor uniformity of surface treatment.

In addition, the average particle size of the boron carbide particles surface-treated with the polyolefin-based resin may be 80 μm to 100 μm. Nano-sizing the size of the boron carbide can improve dispersibility, increase hydrogen density and increase boron content.

The content of boron carbide surface-treated with the polyolefin-based resin may be 1 to 7 parts by weight. If the content of boron carbide surface-treated with the polyolefin-based resin is less than 1 part by weight, neutron shielding performance may be deteriorated, and if it is more than 7 parts by weight, castability and homogeneity with the epoxy resin may be reduced.

Meanwhile, the neutron shielding material composition may include borated graphene and a density increasing agent. Graphene is a carbon allotrope having a structure in which carbon atoms are connected in a hexagonal shape, and has an atomic-level thickness and a large surface area with a two-dimensional plate-like structure, and has excellent mechanical properties, electrical conductivity, and thermal conductivity. In particular, single-layer graphene exhibits low heat generation, excellent charge mobility, current density, chemical resistance, flexibility, elasticity, and excellent thermal conductivity of about 5,000 W/mK.

Meanwhile, graphene is applicable to various fields when it is in the form of an oxide. The graphene can be obtained by exfoliating each graphene layer of graphite, and it is not easy to peel itself due to the van der Waals force between the graphene layers, and it is thermodynamically unstable, resulting in self-aggregation between graphenes. easy to do.

Accordingly, when the graphene is provided in an oxidized form only as an edge, the yield of graphene is increased and mass production is possible, thereby reducing process cost. Preferably, the graphene may be borated graphene. have.

5 is an SEM image of borated graphene according to an embodiment of the present invention.

Referring to FIG. 5, the borated graphene may be dispersed in the neutron shielding material composition in the form of nano-sized particles. When the borated graphene (B-EOG) particles are uniformly dispersed in a nano size in the neutron shielding material composition, thermal conductivity may be greatly improved even with a small content, and at the same time, neutron shielding performance may be maximized.

The density increasing agent increases the specific gravity of the neutron shielding material composition so that it can more effectively shield gamma rays.

In addition, hydrogen content can be increased by substituting a part of the additives other than the epoxy resin, mainly a part of the flame retardant with a density increasing agent. Specifically, when a part of the flame retardant is substituted, since the amount of the epoxy resin can be increased while maintaining the specific gravity of the neutron shielding material composition, a neutron shielding material composition having a high hydrogen content can be prepared, thereby effectively shielding the neutron. can do.

The density increasing agent may be a metal powder, a metal oxide powder, or a mixture thereof. Specifically, the density increasing agent may be Cr, Mn, Fe, Ni, Cu, Sb, U, W, or a mixture thereof having a metal having a melting point of 350°C or higher, and NiO, CuO as a metal oxide having a melting point of 1,000°C or higher. , ZnO, ZrO ₂ , SnO, SnO ₂ , WO ₂ , UO ₂ , PbO, WO ₃ , lanthanide oxides, and mixtures of two or more of them. Of these, Cu, WO ₂ , WO ₃ , ZrO ₂ , and CeO ₂ may be used in consideration of commercial availability.

The average particle size of the density increasing agent is not particularly limited, but if the average particle size is excessively large, the density increasing agent may be precipitated in the preparation of the neutron shielding material composition, so it is preferable to adjust the level to not settle.

The content of the borated graphene and the density increasing agent may be 0.1 to 15 parts by weight. If the content of the borated graphene and the density increasing agent is less than 0.1 part by weight, the thermal conductivity and specific gravity increase effect may be weak, and when it exceeds 15 parts by weight, the viscosity increases, making uniform dispersion difficult, and Since the content is relatively small, the neutron shielding performance may be deteriorated. In addition, the borated graphene and the density increasing agent may be mixed in a weight ratio of 10 to 90: 90 to 10, respectively, and preferably 20 to 80: 80 to 20 in weight ratio.

(Method for manufacturing neutron shielding material composition)

1 is a schematic view showing a method of manufacturing a neutron shielding material composition according to an embodiment of the present invention.

Referring to FIG. 1, a method for manufacturing a neutron shielding material composition according to an embodiment of the present invention includes (a) 20 to 30 parts by weight of an epoxy resin, and aluminum hydroxide and zinc borate 50 surface-treated with a titanium-based or silicon-based surface treatment agent. Preparing a first mixture by mixing ˜65 parts by weight; (b) 10 to 20 parts by weight of the amine curing agent, 1 to 7 parts by weight of boron carbide surface-treated with a polyolefin resin to prepare a second mixture; (c) preparing a third mixture by mixing borated graphene with 0.1-15 parts by weight of a density increasing agent, and 1-10 parts by weight of a dispersing agent; (d) preparing a fourth mixture by mixing 50-60% by weight of the third mixture with the first mixture; (e) mixing the remaining amount of the third mixture and the second mixture to prepare a fifth mixture; (f) mixing the fourth and fifth mixtures.

In the step (a) (S100), the first mixture may be prepared by mixing 20 to 30 parts by weight of the epoxy resin and 50 to 65 parts by weight of aluminum hydroxide and zinc borate surface-treated with a titanium- or silicon-based surface treatment agent. .

The temperature in step (a) (S100) can be adjusted to 35°C to 45°C. When the temperature in the step (a) is less than 35°C, the epoxy resin and the aluminum hydroxide surface-treated with a titanium-based or silicone-based surface treatment agent cannot be uniformly mixed, and if the temperature is higher than 45°C, the viscosity rises to improve workability in a subsequent step. This can degrade.

In addition, the types, contents, functions and roles of the aluminum hydroxide surface-treated with the epoxy resin and titanium- or silicon-based surface treatment agent that can be used in step (a) are the same as described above.

In the step (b) (S200), 10 to 20 parts by weight of the amine-based curing agent, and 1 to 7 parts by weight of boron carbide surface-treated with a polyolefin-based resin may be mixed to prepare a second mixture.

The temperature in step (b) (S200) may be adjusted to 20°C to 30°C. When the temperature of the reactor is less than 20°C, the kneading property of the amine-based curing agent and boron carbide may be lowered, and if it exceeds 30°C, the polyolefin-based resin layer formed on the surface of the boron carbide is damaged or deformed to form the boron carbide. An exposed surface may occur on the surface. That is, the temperature in the step (b) should be adjusted to a certain range so that the polyolefin-based resin layer formed on the surface of the boron carbide administered in the step (b) is not deformed by heat.

In addition, the types, contents, functions, roles, etc. of the amine-based curing agent, polyolefin-based resin, and boron carbide usable in the step (b) are the same as described above.

In the step (c) (S300), the third mixture may be prepared by mixing the borated graphene with 0.1 to 15 parts by weight of the density increasing agent and 1 to 10 parts by weight of the dispersing agent. A certain amount of dispersant may be mixed to improve the density and dispersibility of the borated graphene and the density increasing agent.

Since the borated graphene has a large surface area, kneading properties with other materials may be reduced, and a specific amount of a dispersant may be administered during kneading to improve dispersibility of the borated graphene as well as other components.

The dispersant may be hydrogen peroxide, ethyl alcohol, methyl alcohol, isopropyl alcohol, or a mixture of two or more of them, but is not limited thereto, and the content of the dispersant may be 1 to 10 parts by weight. When the content of the dispersant is out of the above range, the dispersibility of the borated graphene in the neutron shielding material composition may be lowered.

The alcohol-based material used as the dispersant is a volatile material having a low vapor pressure, and can be naturally removed by evaporation in the subsequent steps (d) to (f) after being administered in step (c).

In the steps (d) (S400) and (e) (S500), the fourth and fifth mixtures may be prepared by mixing the first and second mixtures with the third mixture, respectively. The dispersibility of the borated graphene can be improved by administering the third mixture containing the borated graphene to the first and second mixtures instead of collectively.

Meanwhile, in the steps (a) to (f), the mixing may be performed using one or more reactors. Specifically, the steps (a) to (f) may be performed by sequentially introducing the first mixture, the second mixture, the third mixture, the fourth mixture, and the fifth mixture into a single reactor, as required, respectively The steps of may be performed separately in six reactors, two or more steps may be performed in a single reactor, and the other one in a separate reactor.

For example, when using three reactors, steps (a) to (c) are performed in the first to third reactors, respectively, and steps (d) and (e) are respectively the first and second reactors. Step (f) may be performed in the first or second reactor.

Hereinafter, embodiments of the present invention will be described in detail.

(Example 1)

The liquid prepolymer is hydrogenated modified bisphenol A type epoxy resin alkyl C10? Low viscosity 800 cps (25° C.), 28 parts by weight mixed with C15 grisyl ether, and 56 parts by weight of aluminum hydroxide surface-treated with a silicone-based surface treatment agent were mixed in a first reactor in a vacuum controlled at 40° C. to obtain the first mixture. It was prepared.

Triethylene tetraamine, and polyoxy propylenediamine 11 parts by weight of reactants reacted with these curing agents and tall oil fatty acids, and 3 parts by weight of boron carbide surface-treated with polypropylene resin were mixed in a second reactor in a vacuum controlled at 25°C. A second mixture was prepared.

A third mixture was prepared by mixing 2 parts by weight of borated graphene with a density increasing agent and 5 parts by weight of a dispersing agent in a third reactor under vacuum.

Each of the first and second mixtures was mixed with 60% and 40% by weight of the third mixture to prepare a fourth and fifth mixture, and then the fourth and fifth mixtures were mixed to prepare a neutron shielding material composition. Did.

(Example 2)

Except that the polyamidoamine and polyoxypropylenediamine were mixed with 11 parts by weight of the curing agent mixed with 1:1 parts by weight, and the dosage of borated graphene and density increasing agent was adjusted to 1 part by weight, In the same way, a neutron shielding material composition was prepared.

(Example 3)

A neutron shielding material composition was prepared in the same manner as in Example 2, except that the dose of borated graphene and the density increasing agent was adjusted to 0.5 parts by weight.

(Comparative Example 1)

Neutrons were prepared in the same manner as in Example 1, except that 58 parts by weight of aluminum hydroxide and boron carbide, and 3 parts by weight of boron-free graphene, a density increasing agent, and a dispersing agent were not administered. A shielding material composition was prepared.

(Comparative Example 2)

A neutron shielding material in the same manner as in Comparative Example 1, except that 11 parts by weight of polyamidoamine, 58 parts by weight of aluminum hydroxide surface-treated with a titanium-based surface treatment agent, and 3 parts by weight of boron carbide surface-treated with a polypropylene resin were administered. The composition was prepared.

The composition of the neutron shielding material composition prepared according to the above Examples and Comparative Examples is shown in Table 1 below.

ingredient Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Epoxy resin 28.9 28.8 28 28 28 Amine curing agent 11 11 11 11 11 Aluminum hydroxide 56 55 54 58 (no surface treatment) 58 Boron carbide 4 5 6.5 3 3 Borated Grepin 0.1 0.2 0.5 - -

(Unit: parts by weight)

Experimental Example: Evaluation of mechanical properties, heat resistance, and thermal conductivity of the neutron shielding material composition

The mechanical properties, heat resistance, and thermal conductivity of the neutron shielding compositions prepared according to Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated, and the results are shown in Table 2 below.

-Tensile strength: The recognized strength was measured according to ASTM D 638.

-Compressive strength: Compressive strength was measured according to ASTM D695.

-Flexural strength: Flexural strength was measured according to ASTM D790.

-Heat resistance: Relative heat resistance was evaluated by measuring the thermal decomposition temperature with a TGA meter.

-Thermal conductivity: Thermal conductivity was measured by an abnormal heating method using an LFA447 type thermal conductivity meter manufactured by NETZSCH.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 density 1.71 1.67 1.67 1.65 1.69 Tensile strength (kg/mm ² ) 3.59 2.86 2.96 3.2 2.74 Compressive strength (kg/mm ² ) 8.93 13.69 10.32 12.78 15.22 Flexural strength (kg/mm ² ) 5.86 6.41 6.74 6.32 6.12 Thermal conductivity (W/mK) (25℃) 2.82 2.31 1.98 0.65 0.95 Heat resistance 242℃ 240℃ 239℃ 230℃ 234℃

Referring to Table 2, when comparing the mechanical properties, density, heat resistance, and thermal conductivity of Examples 1 to 3 and Comparative Examples 1 and 2, first, mechanical properties, and density are similar results in Examples and Comparative Examples Was confirmed.

However, when comparing the thermal conductivity and heat resistance, Examples 1 to 3 in which borated graphene was administered compared to Comparative Examples 1 and 2 in which it was not administered, the thermal conductivity was significantly improved, and surface-treated aluminum hydroxide and boron carbide were administered. It was confirmed that Examples 1 to 3 had significantly superior heat resistance compared to Comparative Example 1 in which aluminum hydroxide and boron carbide were not treated with surface treatment.

The above description of the present invention is for illustration only, and those skilled in the art to which the present invention pertains can understand that the present invention can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted to be included in the scope of the present invention.

S100: Preparation step of the first mixture
S200: Preparation step of the second mixture
S300: Preparation step of the third mixture
S400: Preparation step of the fourth mixture
S500: Step of preparing the fifth mixture
S600: Manufacturing step of neutron shielding material composition

Claims (10)

Epoxy resin 20-30 parts by weight;
10-20 parts by weight of an amine-based curing agent;
50 to 65 parts by weight of aluminum hydroxide and zinc borate surface-treated with a titanium-based or silicon-based surface treatment agent;
1-7 parts by weight of boron carbide surface-treated with a polyolefin-based resin; And
Borated graphene and a density increasing agent 0.1 to 15 parts by weight; containing,
The density increasing agent is a metal powder, a metal oxide powder or a mixture thereof,
The borated graphene and the density increasing agent are neutron shielding compositions using boron-doped graphene mixed in a weight ratio of 20 to 80:80 to 20, respectively.
The method of claim 1, wherein the epoxy resin is a bisphenol A-type epoxy resin and a hydrogenated epoxy resin, alkyl C10-C15 glycidyl ether (Glycidal ether), characterized in that a mixture of boron doped neutrons using graphene Shielding material composition.
The method according to claim 1, wherein the amine-based curing agent is selected from the group consisting of polyamidoamine, polyetherdiamine, polyoxypropylenediamine, triethylene tetraamine, and reactants reacting these curing agents with tall oil fatty acids, and a mixture of two or more of them. A neutron shielding composition using boron-doped graphene, which is characterized by being one.
The method of claim 1, wherein the average particle size of the aluminum hydroxide surface-treated with the titanium-based surface treatment agent is 1.0 µm to 40 µm, a neutron shielding material composition using boron-doped graphene.
The method of claim 1, wherein the average particle size of the aluminum hydroxide surface-treated with the silicon-based surface treatment agent is a neutron shielding material composition using boron-doped graphene.
The method of claim 1, wherein the polyolefin-based resin is a neutron shielding composition using boron-doped graphene, characterized in that the polypropylene.
The method of claim 1, wherein the density increasing agent is a metal powder, a metal oxide powder, or a mixture thereof, a neutron shielding composition using boron-doped graphene.
(a) preparing a first mixture by mixing 20 to 30 parts by weight of an epoxy resin and 50 to 65 parts by weight of aluminum hydroxide and zinc borate surface-treated with a titanium- or silicon-based surface treatment agent;
(b) 10 to 20 parts by weight of the amine curing agent, 1 to 5 parts by weight of boron carbide surface-treated with a polyolefin resin to prepare a second mixture;
(c) mixing borated graphene with 0.1-15 parts by weight of a density increasing agent, and 1-10 parts by weight of a dispersing agent to prepare a third mixture;
(d) preparing a fourth mixture by mixing 50-60% by weight of the third mixture with the first mixture;
(e) mixing the remaining amount of the third mixture and the second mixture to prepare a fifth mixture;
(f) mixing the fourth and fifth mixtures; a method of manufacturing a neutron shielding material composition using a boron-doped graphene containing.
According to claim 8, Method of manufacturing a neutron shielding material composition using a boron-doped graphene to adjust the temperature in the step (a) to 35 ℃ to 45 ℃.
According to claim 8, Method of manufacturing a neutron shielding material composition using boron doped graphene to control the temperature in step (b) to 20 to 30 ℃.

Images