CN113345615A - Paraffin/boron carbide neutron protection composite material and preparation method thereof - Google Patents
Paraffin/boron carbide neutron protection composite material and preparation method thereof Download PDFInfo
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- CN113345615A CN113345615A CN202110597998.8A CN202110597998A CN113345615A CN 113345615 A CN113345615 A CN 113345615A CN 202110597998 A CN202110597998 A CN 202110597998A CN 113345615 A CN113345615 A CN 113345615A
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/10—Organic substances; Dispersions in organic carriers
- G21F1/103—Dispersions in organic carriers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/26—Bituminous materials, e.g. tar, pitch
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00258—Electromagnetic wave absorbing or shielding materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
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Abstract
The invention discloses a paraffin/boron carbide neutron protection composite material and a preparation method thereof, belongs to the technical field of nuclear protection materials, and solves the problems of incompact tissue, boron carbide settlement and agglomeration and the like in the preparation by a fusion casting method in the prior art. According to the preparation method of the paraffin/boron carbide neutron protection composite material, the content of paraffin in the neutron protection composite material is 1-60 wt%, and the balance is boron carbide, and the paraffin/boron carbide neutron protection composite material is prepared by a cold isostatic pressing method. The invention creatively adopts paraffin and boron carbide as raw materials and adopts a cold isostatic pressing method to prepare the neutron protection composite material. The paraffin/boron carbide neutron protection composite material disclosed by the invention is uniform in boron carbide distribution, compact in structure and excellent in performance, can have the double functions of fast neutron, slow neutron and thermal neutron moderation absorption, and meets the neutron protection requirement of specific occasions of spent fuel aftertreatment.
Description
Technical Field
The invention belongs to the technical field of nuclear protection materials, and relates to a preparation method of a protection material for nuclear radiation places such as nuclear reactor spent fuel assembly storage, radioactive substance storage and transportation and the like, in particular to a paraffin/boron carbide neutron protection composite material and a preparation method thereof.
Background
The nuclear energy is a non-petrochemical energy which is clean, low-carbon, high in supply reliability and capable of being utilized in a large scale, and is an important component in the modern energy system in China. With the rapid development of nuclear power in China, the safe storage, transportation and post-treatment of a large amount of spent fuel become an irremediable problem. The spent fuel contains a large amount of radioactive elements and has strong radioactivity, particularly, in the tail end stage of the spent fuel post-treatment, the spent fuel mainly contains fission elements such as Pu, U, Am, Np, Cm and the like, the fission elements can generate transmutation reaction to generate more fast neutrons, the average energy is about 2MeV, and effective radiation protection must be performed. Shielding against such fast neutrons mainly includes two processes: the fast neutrons are subjected to inelastic scattering with heavy nuclear elements or elastic scattering with light nuclear elements and are moderated into thermal neutrons with lower energy; the thermal neutrons are captured and absorbed by the elements with larger absorption cross sections.
The neutron protection composite material is an important means and carrier for realizing the radiation protection requirements. At present, for neutron protection, the commonly used protective materials mainly include polyolefin-based protective materials such as lead-boron polyethylene and boron-containing polypropylene, boron-containing concrete, boron steel, aluminum-based boron carbide neutron absorbing materials and the like. The polyolefin-based protective material has low softening point and large thermal expansion coefficient, so that the structural stability of the shielding composite material is poor, flammable and explosive substances such as hydrogen, methane and the like can be generated under the irradiation effect, potential safety hazards exist, the preparation process is complex, the process period is long, and the requirements of certain special application occasions on the application flexibility and construction diversity of the shielding material cannot be met. Boron-containing concrete is mainly used for radiation shielding of large-scale protection devices, and the addition of boron can influence the setting and hardening of the concrete and the mechanical properties of the concrete, so that the content of the boron in the concrete cannot be very high, the materials have very high requirements on the forming process and the construction conditions, and the shielding properties of the materials and other physical and mechanical properties are difficult to consider. The boron steel and other metal protection materials have large thickness, large weight and large volume, and neutron irradiation causes irradiation damage inside the materials and deteriorates the performance of the materials. The aluminum-based boron carbide neutron absorbing material has an excellent neutron protection function, but is a neutron protection material aiming at thermal neutron absorption, and has a weak fast neutron protection capability with high energy.
Paraffin is one of materials with excellent neutron moderating effect, and has the advantages of controllable phase change temperature, stable chemical property, low corrosivity, safety, no toxicity, environmental friendliness, good preparation formability, low cost and the like, and B4In C10The thermal neutron absorption cross section of B is as high as 3840barns, is more than 50 times of that of concrete, and can generate in a wide neutron energy range10B(n,α)7The Li transmutation reaction can effectively absorb thermal neutrons, no radioactive isotope is generated during decay after the neutrons are absorbed, the secondary radiation energy is low (0.5MeV), the shielding is easy, and the Li transmutation reaction has the advantages of high melting point, low density, acid and alkali resistance, chemical stability, irradiation resistance, low manufacturing cost and the like. Prepared by effectively compounding paraffin and boron carbideThe neutron protection material can meet the urgent requirements of materials with good moderation absorption/shielding effect, light weight, small volume and radiation resistance in the post-treatment process of the spent fuel.
Disclosure of Invention
Earlier researches of the invention find that the paraffin/boron carbide composite material can be prepared by a fusion casting method. But the paraffin has a density of 0.8-0.9g/cm due to a long solidification period of the molten paraffin3) And density of boron carbide (2.5 g/cm)3) The difference is large, boron carbide is insoluble in paraffin, and the boron carbide can be continuously precipitated in the molten paraffin, so that the uniform distribution of the boron carbide in the paraffin is difficult to realize, and the uniformity of the boron carbide directly influences the physical performance and the protective performance of the neutron moderation absorption dual-function material; in addition, the molten paraffin has larger volume shrinkage during solidification, and the surface and the inside of the paraffin are easy to have hole defects due to overlarge volume change in the casting preparation process, so that the performance is reduced.
One of the purposes of the invention is to provide a preparation method of a paraffin/boron carbide neutron protection composite material, which solves the problems of incompact tissue, boron carbide settlement and agglomeration and the like in the prior art when a fusion casting method is adopted for preparation.
The invention also aims to provide the paraffin/boron carbide neutron protection composite material prepared by the method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a paraffin/boron carbide neutron protection composite material, wherein the content of paraffin in the neutron protection composite material is 1-60 wt%, and the balance is boron carbide, and the preparation method adopts a cold isostatic pressing method.
In some embodiments of the invention, the method comprises the following steps:
s1, powder mixing: evenly mixing paraffin powder and boron carbide powder according to the designed component proportion;
s2, cold isostatic pressing: putting the powder uniformly mixed in the S1 into a die, and preparing the powder into a pressed compact with certain density, strength and shape in a cold isostatic pressing mode;
s3, demolding: and removing the film wrapped outside the pressed compact to obtain the neutron protection composite material.
The method takes the paraffin powder and the boron carbide powder as raw materials, and prepares the neutron protection material capable of realizing the double functions of neutron moderation absorption through two steps of mixing and cold isostatic pressing, the prepared paraffin/boron carbide composite material has uniform components and tissues, the boron carbide is dispersed and distributed, the problems of incompact tissues, boron carbide settlement and agglomeration and the like in the traditional casting method preparation are avoided, the uniform distribution of the boron carbide in the paraffin is realized, the density of the composite material is obviously improved, and the method has the advantages of simple process flow, low production cost, high yield, easy regulation and control of component tissues and the like.
In some embodiments of the invention, the boron carbide powder is a nuclear grade boron carbide powder.
In some embodiments of the present invention, the boron carbide powder has a particle size of 10 to 50 μm.
In some embodiments of the invention, the wax powder has a particle size of 0.1 to 0.5 mm.
In some embodiments of the present invention, in S2, the uniformly mixed powder is filled into a mold, and then vacuum-pumped, sealed, and cold-isostatic pressed.
In some embodiments of the invention, the mold is a soft mold.
In some embodiments of the invention, in the S2, the isostatic cool pressure is 100-250MPa, and the dwell time is 5-30 min.
The invention also provides the paraffin/boron carbide neutron protection composite material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention has scientific design and ingenious conception, creatively adopts paraffin and boron carbide as raw materials, and adopts a cold isostatic pressing method to prepare the neutron protection composite material. The paraffin/boron carbide neutron protection composite material disclosed by the invention is uniform in boron carbide distribution, compact in structure and excellent in performance, can have the double functions of fast neutron, slow neutron and thermal neutron moderation absorption, and meets the neutron protection requirement of specific occasions of spent fuel aftertreatment.
The density of the paraffin/boron carbide neutron protection composite material prepared by the method is close to the theoretical density, and the expansion performance of the paraffin is improved to a great extent by adding the boron carbide.
The method can be used for preparing standard paraffin/boron carbide brick sections, is easy to realize engineering connection operation, and can meet the requirements of application flexibility and construction diversity of shielding materials in certain special application occasions.
The paraffin/boron carbide neutron protection composite material is safe and nontoxic, has low raw material cost, simple preparation process, high yield and high preparation efficiency, and has strong applicability and great economic benefit.
Drawings
FIG. 1 is a microstructure diagram of a paraffin/boron carbide composite material prepared in example 1;
FIG. 2 is a microstructure diagram of a paraffin/boron carbide composite material prepared in a comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment discloses a preparation method of a paraffin/boron carbide neutron protection composite material, which comprises the following steps:
(1) mixing paraffin powder with the granularity of 0.1-0.5 mm and nuclear-grade boron carbide powder with the granularity of 10-50 mu m for 3 hours, wherein the paraffin content is 50 wt%;
(2) and (3) filling the uniformly mixed composite material powder into a cylindrical soft film die with the diameter of 50mm and the height of 100mm, and sealing after air is extracted for 1h by adopting an air extractor. Then preparing the powder into a pressed blank with certain density, strength and shape by a cold isostatic pressing mode, wherein the cold isostatic pressing pressure is 250MPa, and the pressure maintaining time is 5 min;
(3) demolding: and removing the soft film wrapped outside the pressed compact to obtain a paraffin/boron carbide neutron protection composite material finished product.
The density of the paraffin/boron carbide neutron protection composite material prepared by the embodiment is 1.29g/cm3The microstructure is shown in figure 1, and as can be seen from figure 1, the boron carbide in the paraffin/boron carbide neutron protection composite material is uniform in distribution, compact in structure and free of settlement and agglomeration.
Example 2
The embodiment discloses a preparation method of a paraffin/boron carbide neutron protection composite material, which comprises the following steps:
(1) mixing paraffin powder with the granularity of 0.5-1 mm and nuclear-grade boron carbide powder with the granularity of 10-50 mu m for 1h, wherein the paraffin content is 1 wt%;
(2) and (3) filling the uniformly mixed composite material powder into a cylindrical soft film die with the diameter of 50mm and the height of 100mm, and sealing after air is extracted for 1h by adopting an air extractor. Then preparing the powder into a pressed blank with certain density, strength and shape by a cold isostatic pressing mode, wherein the cold isostatic pressing pressure is 100MPa, and the pressure maintaining time is 30 min;
(3) demolding: and removing the soft film wrapped outside the pressed compact to obtain a paraffin/boron carbide neutron protection composite material finished product.
The density of the paraffin/boron carbide neutron protection composite material prepared by the embodiment is 2.35g/cm3The structure is compact, and the boron carbide is uniformly distributed.
Example 3
The embodiment discloses a preparation method of a paraffin/boron carbide neutron protection composite material, which comprises the following steps:
(1) mixing paraffin powder with the granularity of 0.1-0.5 mm and nuclear-grade boron carbide powder with the granularity of 1-10 mu m for 5 hours, wherein the paraffin content is 25 wt%;
(2) and (3) filling the uniformly mixed composite material powder into a cylindrical soft film die with the diameter of 50mm and the height of 100mm, and sealing after air is extracted for 1h by adopting an air extractor. Then preparing the powder into a pressed blank with certain density, strength and shape by a cold isostatic pressing mode, wherein the cold isostatic pressing pressure is 180MPa, and the pressure maintaining time is 18 min;
(3) demolding: and removing the soft film wrapped outside the pressed compact to obtain a paraffin/boron carbide neutron protection composite material finished product.
The density of the paraffin/boron carbide neutron protection composite material prepared by the embodiment is 1.60g/cm3The boron carbide is uniformly distributed and has compact structure.
Example 4
The embodiment discloses a preparation method of a paraffin/boron carbide neutron protection composite material, which comprises the following steps:
(1) mixing paraffin powder with the granularity of 0.1-0.5 mm and nuclear-grade boron carbide powder with the granularity of 50-100 mu m for 5 hours, wherein the paraffin content is 60 wt%;
(2) and (3) filling the uniformly mixed composite material powder into a cylindrical soft film die with the diameter of 50mm and the height of 100mm, and sealing after air is extracted for 1h by adopting an air extractor. Then preparing the powder into a pressed blank with certain density, strength and shape by a cold isostatic pressing mode, wherein the cold isostatic pressing pressure is 250MPa, and the pressure maintaining time is 20 min;
(3) demolding: and removing the soft film wrapped outside the pressed compact to obtain a paraffin/boron carbide neutron protection composite material finished product.
The density of the paraffin/boron carbide neutron protection composite material prepared by the embodiment is 1.09g/cm3The boron carbide is uniformly distributed and has compact structure.
Comparative example 1
In the comparative example, the paraffin/boron carbide composite material is prepared by a fusion casting method and is prepared by the following steps:
(1) heating 50 parts by weight of block paraffin to 80 ℃ for melting, adding 50 parts by weight of 10-50 mu m nuclear-grade boron carbide powder, and fully stirring for 1 h;
(2) slowly pouring the mixed melt of paraffin and boron carbide into a cylindrical stainless steel mold with the diameter of 50mm and the height of 100 mm;
(3) and demolding after the paraffin is fully solidified to obtain the paraffin/boron carbide composite material. This comparative example was madeThe density of the paraffin/boron carbide composite material is 0.88g/cm3The microstructure is shown in figure 2, and it can be seen from figure 2 that boron carbide is agglomerated and segregated, and holes are present in the microstructure.
Finally, it should be noted that: the above embodiments are only preferred embodiments of the present invention to illustrate the technical solutions of the present invention, but not to limit the technical solutions, and certainly not to limit the patent scope of the present invention; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; that is, the technical problems to be solved by the present invention, which are not substantially changed or supplemented by the spirit and the concept of the main body of the present invention, are still consistent with the present invention and shall be included in the scope of the present invention; in addition, the technical scheme of the invention is directly or indirectly applied to other related technical fields, and the technical scheme is included in the patent protection scope of the invention.
Claims (9)
1. The preparation method of the paraffin/boron carbide neutron protection composite material is characterized in that the paraffin content in the neutron protection composite material is 1-60 wt%, the balance is boron carbide, and a cold isostatic pressing method is adopted for preparation.
2. The method of claim 1, comprising the steps of:
s1, powder mixing: evenly mixing paraffin powder and boron carbide powder according to the designed component proportion;
s2, cold isostatic pressing: putting the powder uniformly mixed in the S1 into a die, and preparing the powder into a pressed compact with certain density, strength and shape in a cold isostatic pressing mode;
s3, demolding: and removing the film wrapped outside the pressed compact to obtain the neutron protection composite material.
3. The production method according to claim 2, wherein the boron carbide powder is a nuclear-grade boron carbide powder.
4. The production method according to claim 2, wherein the particle size of the boron carbide powder is 1 to 100 μm.
5. The method according to claim 2, wherein the wax powder has a particle size of 0.1 to 1 mm.
6. The method according to claim 2, wherein in S2, the uniformly mixed powder is charged into a mold, and then vacuum-pumped, sealed and cold-isostatically pressed.
7. The production method according to claim 2 or 3, wherein the mold is a soft mold.
8. The preparation method according to claim 2 or 3, wherein in S2, the cold isostatic pressure is 100MPa and the dwell time is 5-30 min.
9. The paraffin/boron carbide neutron protection composite material prepared by the preparation method of any one of claims 1 to 8.
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Cited By (1)
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| CN115534465A (en) * | 2022-10-26 | 2022-12-30 | 吉林省优点佳信通信科技有限公司 | Shielding film for electromagnetic interference |
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| CN115534465A (en) * | 2022-10-26 | 2022-12-30 | 吉林省优点佳信通信科技有限公司 | Shielding film for electromagnetic interference |
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