CN113201180B - Neutron and gamma ray composite shielding material and preparation method thereof - Google Patents
Neutron and gamma ray composite shielding material and preparation method thereof Download PDFInfo
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- CN113201180B CN113201180B CN202110522142.4A CN202110522142A CN113201180B CN 113201180 B CN113201180 B CN 113201180B CN 202110522142 A CN202110522142 A CN 202110522142A CN 113201180 B CN113201180 B CN 113201180B
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 230000005251 gamma ray Effects 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000006096 absorbing agent Substances 0.000 claims abstract description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 230000007613 environmental effect Effects 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- 239000002244 precipitate Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 28
- 229920001903 high density polyethylene Polymers 0.000 claims description 25
- 239000004700 high-density polyethylene Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- 229910052580 B4C Inorganic materials 0.000 claims description 20
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
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- 238000002156 mixing Methods 0.000 claims description 15
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 13
- 229940075613 gadolinium oxide Drugs 0.000 claims description 13
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 11
- 238000007731 hot pressing Methods 0.000 claims description 11
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- 238000001291 vacuum drying Methods 0.000 claims description 7
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
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- 238000012360 testing method Methods 0.000 description 37
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- 239000004698 Polyethylene Substances 0.000 description 15
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- 238000010438 heat treatment Methods 0.000 description 14
- 239000011133 lead Substances 0.000 description 10
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
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- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
-
- 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
- C08K3/38—Boron-containing compounds
-
- 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
-
- 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
- G21F1/08—Metals; Alloys; Cermets, i.e. sintered mixtures of ceramics and metals
-
- 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
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0887—Tungsten
-
- 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
-
- 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
- C08K2003/2234—Oxides; Hydroxides of metals of lead
-
- 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
-
- 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
- Y02E30/30—Nuclear fission reactors
Abstract
The invention discloses a neutron and gamma ray composite shielding material and a preparation method thereof, wherein the composite shielding material is introduced with a neutron absorber and a gamma absorber which are subjected to surface modification, so that the material has a certain gamma attenuation capacity while having a high-performance neutron absorption capacity; in addition, the interfacial compatibility between the filler and the matrix is improved by coating the surface of the functional filler by the silane coupling agent, the dispersion capacity of the filler in the matrix is improved, and the shielding performance of the material is further improved; the doping of the functional filler also improves the thermal stability and tensile strength of the material to a certain extent. The composite shielding material disclosed by the invention can be applied to high-performance neutron shielding with the environmental temperature lower than 100 ℃ and shielding of a neutron and gamma ray mixed field with a certain limit on bearing load.
Description
Technical Field
The invention relates to a neutron and gamma ray composite shielding material and a preparation method thereof, belonging to the technical field of radiation protection.
Background
In the nuclear-related fields of aerospace, radiomedical treatment, nuclear power generation, military and the like, shielding nuclear radiation is a difficult problem that people cannot escape. The form of nuclear radiation is varied and can be of the particle type (including alpha particles, beta particles, neutrons) or electromagnetic wave type (X-rays and gamma rays). The degree of nuclear radiation hazard is related to the type, energy, irradiation time, absorbed dose and the like of radiation, and can cause direct damage to the reproductive system, immune system, nervous system and the like of a human body. In a plurality of nuclear radiation types, alpha particles and beta particles have large mass, short range and low penetrating power, and common clothes can be blocked and shielded very easily; while neutrons and gamma rays have a strong penetration capacity, special protective measures must be adopted.
Neutrons are electrically neutral particles that are not affected by the coulomb force of the nucleus and the extra-nuclear electrons, and can only slow neutrons by scattering (elastic collisions, inelastic collisions) and various neutron-nuclear reactions to absorb neutrons. The scattering of neutrons refers to the exchange of neutron and target nuclear energy only before and after the neutron and target nuclear act; if the target nuclei do not undergo energy level transitions before and after scattering, the total kinetic energy of neutrons and target systems is unchanged, then the process is called elastic scattering; if the target light absorbs a portion of the kinetic energy for a transition in energy level before and after scattering, the total kinetic energy is reduced, then it is referred to as inelastic scattering. Neutron radiation capture during neutron absorption, nuclear and fission reactions of charged particles, and the like. The high-energy neutrons reduce the energy to the thermal neutron range through elastic collision, and are absorbed through radiation capturing, nuclear reaction and other processes. The probability of each event is related to neutron energy and the number of target nuclei charges. Because the hydrogen nuclear mass is close to the neutron mass, the hydrogen-containing material is an ideal neutron moderator, and polyethylene is used as a high polymer material with the highest hydrogen content, has been widely applied to neutron shielding, and has the advantages of light weight, low price, easy processing and the like. Boron 10 has a relatively high thermal neutron absorption cross section and absorption range, and some boron-containing compounds such as boron carbide, boron nitride, boron oxide, boric acid, etc. are widely used as neutron absorbers. Some rare earth elements such as gadolinium, samarium and europium also have very high thermal neutron absorption cross sections, but the absorption range is not as good as that of boron, but the rare earth elements have very high atomic numbers, if the rare earth elements are used as thermal neutron absorbers, secondary gamma rays emitted by neutron nuclear reaction can be absorbed at the same time, and if the rare earth oxides are used as functional fillers in the composite material, the composite material has certain gamma shielding capacity.
For a long time, the application of nuclear radiation shielding materials has been long, and conventional gamma shielding materials or neutron shielding materials are usually simple metals such as lead, iron, tungsten, cadmium or concrete, polyethylene, paraffin, water and the like, and have a certain protection effect when dealing with a single radiation type; however, in modern radiation protection scenes, the increasingly severe physical environment and the complex radiation environment enable the radiation shielding material to not only need excellent thermodynamic performance, but also consider shielding of a neutron and gamma mixed radiation field; there is also a need for materials with excellent high temperature and radiation resistance in structural components of related nuclear facilities. At present, a single polymer matrix such as polyethylene, epoxy resin and the like hardly meets the severe requirements. Therefore, on the basis of a polymer matrix, according to different application scenes and requirements, different functional fillers are doped into matrix materials, and the preparation of a series of composite materials with excellent shielding performance, excellent thermodynamic performance or long radiation-resistant service life is currently researched and is popular. The research field has important significance for promoting the development of nuclear power and nuclear safety technology industry in China.
Disclosure of Invention
In order to solve the defects and shortcomings of polyethylene shielding materials, the invention aims to provide a neutron and gamma ray composite shielding material and a preparation method thereof. The composite shielding material is an inorganic filler reinforced polyethylene-based composite shielding material. According to the invention, a neutron absorber and a gamma absorber are introduced as functional reinforcing fillers when the polyethylene-based composite shielding material is prepared, so that the capture energy spectrum of the shielding material on neutrons is widened, and the shielding capability of the shielding material on a neutron and gamma mixed radiation field is improved; in addition, the silane coupling agent is adopted in the preparation process, and cladding modification is carried out on the neutron absorber and the gamma absorber, so that the functional filler after cladding modification is easier to disperse in the polymer matrix, and further the action probability of neutrons and gamma photons and the functional filler can be improved, and the shielding performance of the shielding material is improved; in addition, the doping of the filler also improves the thermal stability and the tensile strength of the composite material to a certain extent.
The invention is realized by the following technical scheme:
the formula of the composite shielding material is as follows:
aA+bB+cC+dD
a represents one or more of High Density Polyethylene (HDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), ultra high relative molecular weight polyethylene (UHMWPE);
b represents a neutron absorber or a plurality of neutron absorbers, which are selected from boron carbide (B) 4 C) Boron oxide (B) 2 O 3 ) Boric acid (H) 3 BO 3 ) Elemental boron (B), metallic cadmium (Cd), metallic hafnium (Hf), rare earth elements such as samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy) and oxides thereof;
c represents a gamma absorber or gamma absorbers, which are selected from lead (Pb), lead oxide (PbO), gadolinium oxide (Gd) 2 O 3 ) Tungsten (W), tungsten oxide (WO) 3 ) Bismuth (Bi), bismuth oxide (Bi) 2 O 3 ) Iron (Fe), iron oxide (Fe) 2 O 3 )；
D represents one or more of silane coupling agents; it is for example selected from gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (. Beta. -methoxyethoxy) silane, methylvinyldichlorosilane, methylvinyldimethoxysilane;
a. b, c and d represent the mass fraction of A, B, C, D, respectively; the range is as follows: 30% or more and less than or equal to 100% of a, 0% or less than or equal to 50% of b, 0% or less than or equal to 50% of c, 0% or less than or equal to 5% of d, and b+c >0. The material is applied to high-performance neutron shielding with the environmental temperature lower than 100 ℃ and shielding of a neutron and gamma ray mixed field with limit on bearing load.
The preparation method of the neutron and gamma ray composite shielding material comprises the following steps:
mixing the modified B or unmodified B, the modified C or unmodified C and the powder A; after the material mixing is finished, the mixed powder is placed in a mould, and a release agent or release paper is added for hot pressing; the hot pressing process is that the pre-pressing is carried out for 5 minutes to 20 minutes under the conditions of 0 to 5Mpa and 120 to 180 ℃, the pressing is carried out to 30 to 100Mpa after the temperature is stabilized to 120 to 180 ℃, the constant pressure is carried out for 20 to 180 minutes, then the temperature is increased to 180 to 300 ℃, the pressing is carried out to 40 to 100Mpa, the constant pressure is carried out for 20 to 180 minutes, and then the cooling and the demoulding are carried out, thus obtaining the composite shielding material. The mixing is ball milling mixing. The above step is a hot press molding step of the composite shielding material.
Further, the modified B is milled for 5 minutes to half an hour before mixing.
Further, the modified C is milled for 5 minutes to half an hour prior to mixing.
Further, the modified B is prepared by:
(1) Weighing the components B and D according to the formula;
(2) Dissolving the weighed mass B in a water-ethanol mixed solution with the volume ratio of 1:5 to 1:20, and performing ultrasonic dispersion or stirring for 5 minutes to 1 hour to form a suspension;
(3) Dropwise adding the weighed D into the suspension subjected to ultrasonic dispersion in the step (2), then dropwise adding acetic acid or oxalic acid solution to adjust the pH value in the suspension to 3-5, and stirring the suspension at a constant temperature of 60-120 ℃ for 5-10 hours after the completion of the step;
(4) After the process is finished, separating waste liquid and precipitate by centrifuging the suspension, adding an ethanol solution into the precipitate for alcohol washing, and then taking out the precipitate after alcohol washing, and adding ultrapure water into the precipitate for water washing;
preferably, adding ethanol solution into the precipitate, stirring until the precipitate is uniform, continuing to centrifuge for repeated times until the supernatant is transparent, then taking out the precipitate after alcohol washing, adding ultrapure water, stirring until the precipitate is uniform, and continuing to centrifuge for repeated times until the supernatant is clear;
(5) Vacuum drying the cleaned precipitate at 60-120deg.C for 6-12 hr; or vacuum freeze drying the cleaned precipitate for 12-36 hr to obtain modified B. Grinding the vacuum dried B for 5 minutes to half an hour. The steps (2), (3), (4) and (5) are coating modification steps of the functional filler by using a silane coupling agent.
Further, the modified C is prepared by:
(1) Weighing the components C and D according to the formula;
(2) Dissolving the weighed mass of C in a water-ethanol mixed solution with the volume ratio of 1:5 to 1:20, and performing ultrasonic dispersion or stirring for 5 minutes to 1 hour to form a suspension;
(3) D with good quality is dripped into the suspension liquid after ultrasonic dispersion in the step (2), then the PH value in the suspension liquid is regulated to 3-5 by dripping acetic acid or oxalic acid solution, and after the completion, the suspension liquid is stirred at a constant temperature under the condition of 60-120 ℃ for 5-10 hours;
(4) After the process is finished, separating waste liquid and precipitate by centrifuging the suspension, adding an ethanol solution into the precipitate for alcohol washing, and then taking out the precipitate after alcohol washing, and adding ultrapure water into the precipitate for water washing;
preferably, adding ethanol solution into the precipitate, stirring to uniformity, and centrifuging for multiple times until the supernatant is transparent; taking out the precipitate after alcohol washing, adding ultrapure water, stirring uniformly, and continuing centrifuging for repeated times until the supernatant is clear;
(5) Vacuum drying the cleaned precipitate at 60-120deg.C for 6-12 hr; or vacuum freeze drying the cleaned precipitate for 12-36 hr to obtain modified C.
Grinding the C after vacuum drying for 5 minutes to half an hour. The steps (2), (3), (4) and (5) are coating modification steps of the functional filler by using a silane coupling agent.
The composite shielding material can be applied to high-performance neutron shielding with the environmental temperature lower than 100 ℃ and shielding of a neutron and gamma ray mixed field with a certain limit on the load.
The invention has the advantages that: the neutron absorber is introduced on the basis of polyethylene to improve the energy spectrum range of neutron absorption, the gamma absorber is introduced to improve the shielding capability of the composite material on a neutron and gamma mixed radiation field, meanwhile, the surface modification of functional particles improves the dispersibility of the filler in the matrix, and the doping of the filler also improves the thermal stability and the tensile strength of the composite material to a certain extent.
Detailed Description
The invention is described in detail in the following specific examples. The following examples are intended to be illustrative only and the scope of the invention is to be construed as including the full breadth of the claims and by the recitation of the following examples, the full breadth of the claims can be fully set forth by those skilled in the art.
Example 1:
32g of gadolinium oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic day and placed in a closed container. Take out 32g Gd 2 O 3 The powder was placed in a beaker, 100ml of absolute ethyl alcohol and 10ml of ultrapure water were added, and after stirring uniformly, the powder was placed in an ultrasonic apparatus for ultrasonic dispersion for 10 minutes. After the completion of the ultrasonic treatment, 3.2ml of gamma-methacryloxypropyl trimethoxysilane was added dropwise to the beaker, followed by dropwise addition of an acetic acid solution, and the PH value of the mixed solution was measured by a PH meter during the dropwise addition until ph=3, and the dropwise addition operation was ended. The beaker solution was transferred to a three-necked flask in an oil bath, and stirred at constant temperature of 80℃for 10 hours. After completion, filling the mixed solution in the flask into test tubes in batches, centrifuging for 5 minutes at 8000r/min by using a centrifuge, pouring the centrifuged test tube upper liquid into a waste liquid barrel, adding ethanol into the test tubes filled with sediment, stirring until the mixture is uniform, and continuing centrifuging for 2-5 times until the test tube upper liquid is transparent; and then adding ultrapure water for water washing and centrifuging operation, stirring until uniformity, continuing centrifuging for 2-5 times until the supernatant of the test tube is clear, and removing excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was placed in a vacuum drying oven and dried under vacuum at 80℃for 12 hours.
Taking out the dried modified Gd 2 O 3 Powder, hereinafter referred to as MO-Gd 2 O 3 . Grinding for 10 min by using a grinding bowl, and grinding 32g of MO-Gd 2 O 3 Powder, 32g boron carbide powder256g of high-density polyethylene powder are put into a charging barrel of a mixer together, grinding balls are added, and mixing is carried out for 30 minutes under the condition of 100 r/min. The mixed powder was then transferred to a hot press die and hot pressed with polytetrafluoroethylene release paper. Before hot pressing, the upper and lower heating plates of the hot press are required to reach the preset temperature of 120 ℃, after preheating, the heat-insulating gloves are worn, the mould is placed between the upper and lower heating plates, and the mould is pre-pressed for 5 minutes under the pressure of 2 Mpa. After the prepressing is finished, the pressurizing rod is rocked to pressurize to 30Mpa, the temperature is set to 120 ℃, and the heat preservation and the pressure maintaining are carried out for 20 minutes; then pressurizing to 40Mpa, setting the temperature to 180 ℃, and preserving heat and pressure for 30 minutes.
After the process is finished, cooling, pressure relief and demoulding are carried out. The prepared MO-Gd can be obtained 2 O 3 /B 4 C/HDPE composite shielding material.
The neutron shielding performance test is carried out on the prepared material by using a Cf-252 neutron source, a polyethylene shielding cylinder and a shielding performance test device built by a high-sensitivity neutron dose measuring instrument, and the measured neutron shielding rates are 38.93%, 57.42%, 68.61%, 76.86%, 81.71%, 85.34%, 90.93%, 92.75%, 93.97% and 94.17% when the thicknesses of the material are 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm respectively.
The gamma shielding performance test device constructed by using the Cs-137 gamma source, the lead chamber and the gamma radiation dosimeter was used for testing the gamma shielding performance of the prepared material, and the measured gamma shielding rates were 10.36%, 21.41%, 31.17%, 38.81%, 45.53%, 51.20%, 56.55%, 61.75%, 64.79% and 67.90% when the thicknesses of the materials were 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, respectively.
Example 2:
32g of lead oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic day and placed in a closed container. Taking out 32g of PbO powder, putting into a beaker, adding 100ml of absolute ethyl alcohol and 10ml of ultrapure water, stirring uniformly, and then putting into an ultrasonic instrument for ultrasonic dispersion for 10 minutes. After the completion of the ultrasonic treatment, 3.2ml of gamma-methacryloxypropyl trimethoxysilane was added dropwise to the beaker, followed by dropwise addition of an acetic acid solution, and the PH value of the mixed solution was measured by a PH meter during the dropwise addition until ph=3, and the dropwise addition operation was ended. The beaker solution was transferred to a three-necked flask in an oil bath, and stirred at constant temperature of 80℃for 10 hours. After completion, filling the mixed solution in the flask into test tubes in batches, centrifuging for 5 minutes at 8000r/min by using a centrifuge, pouring the centrifuged test tube upper liquid into a waste liquid barrel, adding ethanol into the test tubes filled with sediment, stirring until the mixture is uniform, and continuing centrifuging for 2-5 times until the test tube upper liquid is transparent; and then adding ultrapure water for water washing and centrifuging operation, stirring until uniformity, continuing centrifuging for 2-5 times until the supernatant of the test tube is clear, and removing excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was dried in a vacuum oven at 80℃for 12 hours under vacuum.
Taking out the dried modified PbO powder, and short for MO-PbO. Grinding for 10 min by using a grinding bowl, putting 32g of ground MO-PbO powder, 32g of boron carbide powder and 256g of high-density polyethylene powder into a charging barrel of a mixer, adding grinding balls, and mixing for 30 min under the condition of 100 r/min. The mixed powder was then transferred to a hot press die and hot pressed with polytetrafluoroethylene release paper. Before hot pressing, the upper and lower heating plates of the hot press are required to reach the preset temperature of 120 ℃, after preheating, the heat-insulating gloves are worn, the mould is placed between the upper and lower heating plates, and the mould is pre-pressed for 5 minutes under the pressure of 2 Mpa. After the prepressing is finished, the pressurizing rod is rocked to pressurize to 30Mpa, the temperature is set to 120 ℃, and the heat preservation and the pressure maintaining are carried out for 20 minutes; then pressurizing to 40Mpa, setting the temperature to 180 ℃, and preserving heat and pressure for 30 minutes.
After the process is finished, cooling, pressure relief and demoulding are carried out. The prepared MO-PbO/B can be obtained 4 C/HDPE composite shielding material.
The neutron shielding performance test is carried out on the prepared material by using a Cf-252 neutron source, a polyethylene shielding cylinder and a shielding performance test device built by a high-sensitivity neutron dose measuring instrument, and the measured neutron shielding rates are 36.25%, 54.34%, 64.61%, 72.97%, 79.74%, 84.34%, 88.19%, 88.48%, 90.51% and 92.27% when the thicknesses of the materials are 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm respectively.
The gamma shielding performance test device constructed by using the Cs-137 gamma source, the lead chamber and the gamma radiation dosimeter is used for testing the gamma shielding performance of the prepared material, and the measured gamma shielding rates are 14.39%, 23.17%, 31.24%, 38.75%, 44.29%, 51.30%, 56.29%, 60.13%, 62.42% and 65.90% when the thicknesses of the materials are 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm respectively.
Example 3:
32g of tungsten powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic day and placed in a closed container. Taking out 32g tungsten powder, putting into a beaker, adding 100ml absolute ethyl alcohol and 10ml ultrapure water, uniformly stirring, and then putting into an ultrasonic instrument for ultrasonic dispersion for 10 minutes. After the completion of the ultrasonic treatment, 3.2ml of gamma-methacryloxypropyl trimethoxysilane was added dropwise to the beaker, followed by dropwise addition of an acetic acid solution, and the PH value of the mixed solution was measured by a PH meter during the dropwise addition until ph=3, and the dropwise addition operation was ended. The beaker solution was transferred to a three-necked flask in an oil bath, and stirred at constant temperature of 80℃for 10 hours. After completion, filling the mixed solution in the flask into test tubes in batches, centrifuging for 5 minutes at 8000r/min by using a centrifuge, pouring the centrifuged test tube upper liquid into a waste liquid barrel, adding ethanol into the test tubes filled with sediment, stirring until the mixture is uniform, and continuing centrifuging for 2-5 times until the test tube upper liquid is transparent; and then adding ultrapure water for water washing and centrifuging operation, stirring until uniformity, continuing centrifuging for 2-5 times until the supernatant of the test tube is clear, and removing excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was dried in a vacuum oven at 80℃for 12 hours under vacuum.
The dried modified W is taken out and referred to as MO-W hereinafter. Grinding for 10 min by using a grinding bowl, putting 32g of ground MO-W powder, 32g of boron carbide powder and 256g of high-density polyethylene powder into a charging barrel of a mixer, adding grinding balls, and mixing for 30 min under the condition of 100 r/min. The mixed powder was then transferred to a hot press die and hot pressed with polytetrafluoroethylene release paper. Before hot pressing, the upper and lower heating plates of the hot press are required to reach the preset temperature of 120 ℃, after preheating, the heat-insulating gloves are worn, the mould is placed between the upper and lower heating plates, and the mould is pre-pressed for 5 minutes under the pressure of 2 Mpa. After the prepressing is finished, the pressurizing rod is rocked to pressurize to 30Mpa, the temperature is set to 120 ℃, and the heat preservation and the pressure maintaining are carried out for 20 minutes; then pressurizing to 40Mpa, setting the temperature to 180 ℃, and preserving heat and pressure for 30 minutes.
After the process is finished, cooling, pressure relief and demoulding are carried out. The prepared MO-W/B can be obtained 4 C/HDPE composite shielding material.
The neutron shielding performance test device built by the Cf-252 neutron source, the polyethylene shielding cylinder and the high-sensitivity neutron dosimeter is used for carrying out neutron shielding performance test on the prepared material, and when the thicknesses of the material are respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured neutron shielding rates are respectively 38.46%, 53.94%, 62.91%, 73.86%, 79.25%, 86.04%, 88.27%, 89.17%, 91.34% and 92.59%.
The gamma shielding performance test device constructed by using the Cs-137 gamma source, the lead chamber and the gamma radiation dosimeter is used for testing the gamma shielding performance of the prepared material, and the measured gamma shielding rates are 18.64%, 29.83%, 38.29%, 44.48%, 50.39%, 56.14%, 62.80%, 65.89%, 69.42% and 73.37% when the thicknesses of the materials are 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm respectively.
Example 4:
64g of gadolinium oxide powder, 32g of boron carbide powder and 224g of high-density polyethylene powder are weighed by an electronic day and placed in a closed container. Take out 64g Gd 2 O 3 The powder was placed in a beaker, 100ml of absolute ethyl alcohol and 10ml of ultrapure water were added, and after stirring uniformly, the powder was placed in an ultrasonic apparatus for ultrasonic dispersion for 10 minutes. After the completion of the sonication, 3.2ml of gamma-methacryloxypropyl tris (propyl) was added dropwise to the beakerAnd (3) methoxy silane, then dropwise adding acetic acid solution, and measuring the pH value of the mixed solution by using a pH meter in the dropwise adding process until the pH=3, and ending the dropwise adding operation. The beaker solution was transferred to a three-necked flask in an oil bath, and stirred at constant temperature of 80℃for 10 hours. After completion, filling the mixed solution in the flask into test tubes in batches, centrifuging for 5 minutes at 8000r/min by using a centrifuge, pouring the centrifuged test tube upper liquid into a waste liquid barrel, adding ethanol into the test tubes filled with sediment, stirring until the mixture is uniform, and continuing centrifuging for 2-5 times until the test tube upper liquid is transparent; and then adding ultrapure water for water washing and centrifuging operation, stirring until uniformity, continuing centrifuging for 2-5 times until the supernatant of the test tube is clear, and removing excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was placed in a vacuum drying oven and dried under vacuum at 80℃for 12 hours.
Taking out the dried modified Gd 2 O 3 Powder, hereinafter referred to as MO-Gd 2 O 3 . Grinding for 10 min by using a grinding bowl, and grinding 64g of MO-Gd 2 O 3 The powder, 32g of boron carbide powder and 224g of high-density polyethylene powder are put together into a cylinder of a mixer, and grinding balls are added to mix for 30 minutes at 100 r/min. The mixed powder was then transferred to a hot press die and hot pressed with polytetrafluoroethylene release paper. Before hot pressing, the upper and lower heating plates of the hot press are required to reach the preset temperature of 120 ℃, after preheating, the heat-insulating gloves are worn, the mould is placed between the upper and lower heating plates, and the mould is pre-pressed for 5 minutes under the pressure of 2 Mpa. After the prepressing is finished, the pressurizing rod is rocked to pressurize to 30Mpa, the temperature is set to 120 ℃, and the heat preservation and the pressure maintaining are carried out for 20 minutes; then pressurizing to 40Mpa, setting the temperature to 180 ℃, and preserving heat and pressure for 30 minutes.
After the process is finished, cooling, pressure relief and demoulding are carried out. The prepared MO-Gd can be obtained 2 O 3 /B 4 C/HDPE composite shielding material.
The neutron shielding performance test is carried out on the prepared material by using a Cf-252 neutron source, a polyethylene shielding cylinder and a shielding performance test device built by a high-sensitivity neutron dose measuring instrument, and the measured neutron shielding rates are 38.77%, 56.53%, 62.07%, 72.84%, 79.51%, 84.77%, 87.14%, 89.79%, 91.33% and 92.61% when the thicknesses of the materials are 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm respectively.
The gamma shielding performance test device constructed by using the Cs-137 gamma source, the lead chamber and the gamma radiation dosimeter was used for testing the gamma shielding performance of the prepared material, and the measured gamma shielding rates were 13.37%, 24.88%, 34.04%, 41.31%, 48.33%, 54.09%, 59.39%, 64.86%, 68.19% and 72.08% when the thicknesses of the materials were 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, respectively.
Example 5:
32g of gadolinium oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic day and placed in a closed container. Take out 32g B 4 The powder C is placed in a beaker, 100ml of absolute ethyl alcohol and 10ml of ultrapure water are added, and after being stirred uniformly, the powder C is placed in an ultrasonic instrument for ultrasonic dispersion, and the time is set for 10 minutes. After the completion of the ultrasonic treatment, 3.2ml of gamma-aminopropyl triethoxysilane was added dropwise to the beaker, and then acetic acid solution was added dropwise thereto, and the PH value of the mixed solution was measured by a PH meter during the dropwise addition until ph=3, and the dropwise addition operation was ended. The beaker solution was transferred to a three-necked flask in an oil bath, and stirred at constant temperature of 80℃for 10 hours. After completion, filling the mixed solution in the flask into test tubes in batches, centrifuging for 5 minutes at 8000r/min by using a centrifuge, pouring the centrifuged test tube upper liquid into a waste liquid barrel, adding ethanol into the test tubes filled with sediment, stirring until the mixture is uniform, and continuing centrifuging for 2-5 times until the test tube upper liquid is transparent; and then adding ultrapure water for water washing and centrifuging operation, stirring until uniformity, continuing centrifuging for 2-5 times until the supernatant of the test tube is clear, and removing excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was dried in a vacuum oven at 80℃for 12 hours under vacuum.
Taking out the dried modified B 4 Powder C, hereinafter referred to as MO-B 4 C. By means of grinding bowl pairsGrinding the modified powder for 10 min, and grinding 32g of ground MO-B 4 Powder C, 32gGd 2 O 3 The powder was placed in a cylinder of a mixer together with 256g of high-density polyethylene powder, and grinding balls were added thereto, and mixed at 100r/min for 30 minutes. The mixed powder was then transferred to a hot press die and hot pressed with polytetrafluoroethylene release paper. Before hot pressing, the upper and lower heating plates of the hot press are required to reach the preset temperature of 120 ℃, after preheating, the heat-insulating gloves are worn, the mould is placed between the upper and lower heating plates, and the mould is pre-pressed for 5 minutes under the pressure of 2 Mpa. After the prepressing is finished, the pressurizing rod is rocked to pressurize to 30Mpa, the temperature is set to 120 ℃, and the heat preservation and the pressure maintaining are carried out for 20 minutes; then pressurizing to 40Mpa, setting the temperature to 180 ℃, and preserving heat and pressure for 30 minutes.
After the process is finished, cooling, pressure relief and demoulding are carried out. The prepared Gd can be obtained 2 O 3 /MO-B 4 C/HDPE composite shielding material.
The neutron shielding performance test device built by the Cf-252 neutron source, the polyethylene shielding cylinder and the high-sensitivity neutron dosimeter is used for carrying out neutron shielding performance test on the prepared material, and when the thicknesses of the material are respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured neutron shielding rates are respectively 35.56%, 58.92%, 67.35%, 75.29%, 77.37%, 83.22%, 85.71%, 89.52%, 90.81% and 91.93%.
The gamma shielding performance test device constructed by using the Cs-137 gamma source, the lead chamber and the gamma radiation dosimeter is used for testing the gamma shielding performance of the prepared material, and the measured gamma shielding rates are respectively 10.80%, 19.29%, 28.57%, 35.83%, 41.58%, 49.28%, 52.14%, 57.89%, 61.85% and 64.99% when the thicknesses of the materials are respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15 cm.
Example 6:
32g of gadolinium oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic day divider, and 32g of Gd is weighed 2 O 3 Powder, 32g B 4 Powder C together with 256g of high-density polyethylene powderPlacing into a charging barrel of a mixer, adding grinding balls, and mixing for 30 minutes under the condition of 100 r/min. The mixed powder was then transferred to a hot press die and hot pressed with polytetrafluoroethylene release paper. Before hot pressing, the upper and lower heating plates of the hot press are required to reach the preset temperature of 120 ℃, after preheating, the heat-insulating gloves are worn, the mould is placed between the upper and lower heating plates, and the mould is pre-pressed for 5 minutes under the pressure of 2 Mpa. After the prepressing is finished, the pressurizing rod is rocked to pressurize to 30Mpa, the temperature is set to 120 ℃, and the heat preservation and the pressure maintaining are carried out for 20 minutes; then pressurizing to 40Mpa, setting the temperature to 180 ℃, and preserving heat and pressure for 30 minutes.
After the process is finished, cooling, pressure relief and demoulding are carried out. The prepared Gd can be obtained 2 O 3 /B 4 C/HDPE composite shielding material.
The neutron shielding performance test is carried out on the prepared material by using a Cf-252 neutron source, a polyethylene shielding cylinder and a shielding performance test device built by a high-sensitivity neutron dose measuring instrument, and the measured neutron shielding rates are 34.72%, 57.39%, 65.46%, 74.28%, 76.42%, 82.11%, 84.87%, 88.02%, 89.77% and 90.02% when the thicknesses of the materials are 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm respectively.
The gamma shielding performance test device constructed by using the Cs-137 gamma source, the lead chamber and the gamma radiation dosimeter is used for testing the gamma shielding performance of the prepared material, and the measured gamma shielding rates are respectively 10.83%, 19.94%, 28.53%, 35.19%, 41.62%, 49.77%, 52.38%, 57.24%, 61.22% and 64.13% when the thicknesses of the materials are respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15 cm.
Example 7:
32g of gadolinium oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic day and placed in a closed container. Take out 32g Gd 2 O 3 The powder was placed in a beaker, 100ml of absolute ethyl alcohol and 10ml of ultrapure water were added, and after stirring uniformly, the powder was placed in an ultrasonic apparatus for ultrasonic dispersion for 10 minutes. After the completion of the ultrasonic treatment, 3.2ml of gamma-methyl propylene was added dropwise to the beakerThe acyloxypropyl trimethoxysilane was then added dropwise with acetic acid solution, and the PH value of the mixed solution was measured by a PH meter during the addition until ph=3, and the addition was completed. The beaker solution was transferred to a three-necked flask in an oil bath, and stirred at constant temperature of 80℃for 10 hours. After completion, filling the mixed solution in the flask into test tubes in batches, centrifuging for 5 minutes at 8000r/min by using a centrifuge, pouring the centrifuged test tube upper liquid into a waste liquid barrel, adding ethanol into the test tubes filled with sediment, stirring until the mixture is uniform, and continuing centrifuging for 2-5 times until the test tube upper liquid is transparent; and then adding ultrapure water for water washing and centrifuging operation, stirring until uniformity, continuing centrifuging for 2-5 times until the supernatant of the test tube is clear, and removing excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was dried in a vacuum oven at 80℃for 12 hours under vacuum.
The step B is adopted 4 The powder C is treated identically to obtain the modified B 4 And C, powder.
Taking out the dried modified Gd 2 O 3 Powder and modification B 4 C powder, hereinafter referred to as MO-Gd 2 O 3 And MO-B 4 C. Two modified powders were ground with a grinding bowl for 10 minutes, respectively, and 32g of ground MO-Gd was removed 2 O 3 Powder, 32g of ground MO-B 4 The powder C and 256g of high-density polyethylene powder are put into a charging barrel of a mixer together, grinding balls are added, and mixing is carried out for 30 minutes under the condition of 100 r/min. The mixed powder was then transferred to a hot press die and hot pressed with polytetrafluoroethylene release paper. Before hot pressing, the upper and lower heating plates of the hot press are required to reach the preset temperature of 120 ℃, after preheating, the heat-insulating gloves are worn, the mould is placed between the upper and lower heating plates, and the mould is pre-pressed for 5 minutes under the pressure of 2 Mpa. After the prepressing is finished, the pressurizing rod is rocked to pressurize to 30Mpa, the temperature is set to 120 ℃, and the heat preservation and the pressure maintaining are carried out for 20 minutes; then pressurizing to 40Mpa, setting the temperature to 180 ℃, and preserving heat and pressure for 30 minutes.
After the process is finished, cooling, pressure relief and demoulding are carried out. The prepared MO-Gd can be obtained 2 O 3 /MO-B 4 C/HDPE composite shielding material.
The neutron shielding performance test device built by the Cf-252 neutron source, the polyethylene shielding cylinder and the high-sensitivity neutron dosimeter is used for carrying out neutron shielding performance test on the prepared material, and when the thicknesses of the material are respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured neutron shielding rates are respectively 37.65%, 60.64%, 68.46%, 77.74%, 79.27%, 85.45%, 87.98%, 91.18%, 92.49% and 93.94%.
The gamma shielding performance test device constructed by using the Cs-137 gamma source, the lead chamber and the gamma radiation dosimeter was used for testing the gamma shielding performance of the prepared material, and the measured gamma shielding rates were 12.70%, 21.87%, 30.64%, 37.63%, 43.74%, 51.60%, 54.69%, 59.75%, 65.26% and 67.93% when the thicknesses of the materials were 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, respectively.
The above examples are merely illustrative of preferred embodiments of the invention, which are not exhaustive of all details, nor are they intended to limit the invention to the particular embodiments disclosed. Various modifications and improvements of the technical scheme of the present invention will fall within the protection scope of the present invention as defined in the claims without departing from the design spirit of the present invention.
Claims (3)
1. The preparation method of the neutron and gamma ray composite shielding material is characterized in that the composite shielding material is applied to high-performance neutron shielding with the environmental temperature lower than 100 ℃ and shielding of a neutron and gamma ray mixed field with the limit on bearing load; the preparation method comprises the following raw materials: 32g of gadolinium oxide powder, 32g of boron carbide powder, 256g of high density polyethylene powder and 6.4 ml gamma-methacryloxypropyl trimethoxysilane;
the preparation method comprises the following steps:
the modified neutron absorber boron carbide was prepared by:
(1) Weighing neutron absorber boron carbide and silane coupling agent gamma-methacryloxypropyl trimethoxysilane;
(2) Dissolving the weighed neutron absorber boron carbide in a water-ethanol mixed solution with the volume ratio of 1:5 to 1:20, and performing ultrasonic dispersion or stirring for 5 minutes to 1 hour to form a suspension;
(3) Dropwise adding weighed silane coupling agent gamma-methacryloxypropyl trimethoxy silane into the suspension well dispersed in the step (2), then dropwise adding acetic acid or oxalic acid solution to adjust the pH value in the suspension to 3-5, and stirring the suspension at a constant temperature of 60-120 ℃ for 5-10 hours after the completion of the step, wherein the dosage of the silane coupling agent gamma-methacryloxypropyl trimethoxy silane is 3.2ml;
(4) After the process is finished, separating waste liquid and precipitate by centrifuging the suspension, adding an ethanol solution into the precipitate for alcohol washing, and then taking out the precipitate after alcohol washing, and adding ultrapure water into the precipitate for water washing;
(5) Vacuum drying the cleaned precipitate at 60-120deg.C for 6-12 hr; preparing modified neutron absorber boron carbide;
the modified gamma absorber gadolinium oxide was prepared by:
(a) Weighing a gamma absorbent gadolinium oxide and a silane coupling agent gamma-methacryloxypropyl trimethoxy silane component;
(b) Dissolving weighed gamma absorbent gadolinium oxide in a water-ethanol mixed solution with the volume ratio of 1:5 to 1:20, and performing ultrasonic dispersion or stirring for 5 minutes to 1 hour to form a suspension;
(c) Dropwise adding weighed silane coupling agent gamma-methacryloxypropyl trimethoxy silane into the suspension well dispersed in the step (b), then dropwise adding acetic acid or oxalic acid solution to adjust the pH value in the suspension to 3-5, and stirring the suspension at a constant temperature of 60-120 ℃ for 5-10 hours after the completion of the step, wherein the dosage of the silane coupling agent gamma-methacryloxypropyl trimethoxy silane is 3.2ml;
(d) After the process is finished, separating waste liquid and precipitate by centrifuging the suspension, adding an ethanol solution into the precipitate for alcohol washing, and then taking out the precipitate after alcohol washing, and adding ultrapure water into the precipitate for water washing;
(e) Vacuum drying the cleaned precipitate at 60-120deg.C for 6-12 hr; preparing modified gamma absorbent gadolinium oxide;
ball-milling and mixing three powders of modified neutron absorber boron carbide, modified gamma absorber gadolinium oxide and high-density polyethylene; after the material mixing is finished, the mixed powder is placed in a mould, and a release agent or release paper is added for hot pressing; the hot pressing process is that the pre-pressing is carried out for 5 minutes to 20 minutes under the conditions of more than 0 and less than or equal to 5Mpa and 120 ℃ to 180 ℃, the pressing is carried out to 30 to 100Mpa after the temperature is stabilized to 120 ℃ to 180 ℃ and the constant pressure is carried out for 20 to 180 minutes, then the temperature is increased to 180 ℃ to 300 ℃ and the pressing is carried out to 40 to 100Mpa and the constant pressure is carried out for 20 to 180 minutes, and then the cooling and the demoulding are carried out, thus obtaining the composite shielding material.
2. The method of claim 1, wherein the modified neutron absorber boron carbide is milled for 5 minutes to half an hour prior to mixing.
3. The method of claim 1, wherein the modified gamma absorber gadolinium oxide is milled for 5 minutes to half an hour prior to mixing.
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