CN113201180A - 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
- Publication number
- CN113201180A CN113201180A CN202110522142.4A CN202110522142A CN113201180A CN 113201180 A CN113201180 A CN 113201180A CN 202110522142 A CN202110522142 A CN 202110522142A CN 113201180 A CN113201180 A CN 113201180A
- Authority
- CN
- China
- Prior art keywords
- precipitate
- neutron
- gamma
- minutes
- shielding material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 230000005251 gamma ray Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000012767 functional filler Substances 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 239000002244 precipitate Substances 0.000 claims description 50
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 239000006228 supernatant Substances 0.000 claims description 26
- 229910052580 B4C Inorganic materials 0.000 claims description 25
- 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 25
- 229920001903 high density polyethylene Polymers 0.000 claims description 25
- 239000004700 high-density polyethylene Substances 0.000 claims description 25
- -1 polyethylene Polymers 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 20
- 239000012498 ultrapure water Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 238000007731 hot pressing Methods 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 17
- 239000006096 absorbing agent Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- 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 7
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 7
- 229940075613 gadolinium oxide Drugs 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000000945 filler Substances 0.000 abstract description 5
- 239000002250 absorbent Substances 0.000 abstract description 4
- 230000002745 absorbent Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 28
- 238000011056 performance test Methods 0.000 description 28
- 230000005855 radiation Effects 0.000 description 27
- 235000019441 ethanol Nutrition 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000227 grinding Methods 0.000 description 10
- 239000011133 lead Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000009413 insulation Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 5
- 238000003801 milling Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 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
- 230000000694 effects Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 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
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000903 blocking effect Effects 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
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000004992 fission Effects 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
- 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
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 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
- 239000000126 substance Substances 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 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 a neutron absorbent and a gamma absorbent which are subjected to surface modification are introduced into the composite shielding material, so that the material has high-performance neutron absorption capacity and also has certain gamma attenuation capacity; in addition, the silane coupling agent coats the surface of the functional filler, so that the interface compatibility between the filler and the matrix is improved, 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 ambient temperature lower than 100 ℃ and shielding of a neutron and gamma ray mixed field with 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 fields of aerospace, radiation medicine, nuclear power generation, military and the like, shielding of nuclear radiation is a difficult problem which cannot be avoided by people. The form of nuclear radiation is diverse and can be of the particle type (including alpha particles, beta particles, neutrons) or the electromagnetic wave type (X-rays and gamma rays). The degree of nuclear radiation damage is related to the type, energy, irradiation time, absorbed dose and the like of radiation, and can cause direct damage to the reproductive system, the immune system, the nervous system and the like of a human body. Among many nuclear radiation types, alpha particles and beta particles have large mass, short range and low penetrating power, so that common clothes can be used for blocking, and the shielding is very simple; neutrons and gamma rays have strong penetrating power, and special protection measures must be adopted.
Neutrons are electrically neutral particles that are not affected by coulomb forces of the nuclei and extra-nuclear electrons, but absorb neutrons only by scattering (elastic collisions, inelastic collisions) to slow down the neutrons and various neutron-nuclear reactions. The scattering of neutrons refers to the exchange of energy between neutrons and target nuclei only before and after the neutrons and the target nuclei act; elastic scattering is called if the target nuclei do not undergo transitions in energy level before and after scattering, and the total kinetic energy of neutrons and the target nuclei system before and after scattering is unchanged; inelastic scattering is called if the target nuclei absorb a portion of the kinetic energy for a transition at an energy level before and after scattering and the total kinetic energy is reduced. The absorption process of neutrons includes the radiation capture of neutrons, the nuclear reaction and fission reaction of charged particles, and the like. High-energy neutrons reduce energy to the thermal neutron range through elastic collision, and are absorbed through processes such as radiation capture, nuclear reaction and the like. The probability of each effect is related to the neutron energy and the nuclear charge number of the target atom. The quality of hydrogen nuclei is close to that of neutrons, so that the hydrogen-containing material is an ideal neutron moderator, polyethylene is used as a high polymer material with the highest hydrogen content and is widely applied to neutron shielding, and the polyethylene also has the advantages of light weight, low price, easiness in processing and the like. Boron 10 has a high thermal neutron absorption cross section and absorption range, and some boron-containing compounds such as boron carbide, boron nitride, boron oxide, boric acid and the like are widely applied to neutron absorbers. Some rare earth elements such as gadolinium, samarium and europium also have high thermal neutron absorption cross sections, but the absorption ranges are not as good as boron, but the rare earth elements have high atomic numbers, and if the rare earth elements are used as a thermal neutron absorber, 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 a composite material, the rare earth elements have certain gamma shielding capacity.
Since long, the traditional gamma shielding material or neutron shielding material is usually a metal simple substance such as lead, iron, tungsten, cadmium or concrete, polyethylene, paraffin, water, etc., and these materials have a certain protection effect when dealing with a single radiation type; however, in modern radiation protection scenes, due to increasingly severe physical environments and complex radiation environments, the radiation shielding material not only needs excellent thermodynamic performance, but also can shield a neutron and gamma mixed radiation field; there is also a need for materials having excellent high temperature and radiation resistance in structural components of associated nuclear facilities. At present, the single polymer matrix such as polyethylene, epoxy resin and the like can hardly meet the above severe requirements. Therefore, on the basis of a polymer matrix, according to different application scenes and requirements, different functional fillers are doped into a matrix material to prepare a series of composite materials with excellent shielding performance, excellent thermodynamic performance or long radiation-resistant service life. The research field has important significance for promoting the development of nuclear power and nuclear safety technical career in China.
Disclosure of Invention
In order to solve the defects 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, the neutron absorber and the 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 to neutrons is widened, and the shielding capability of the shielding material to a neutron and gamma mixed radiation field is improved; in addition, the silane coupling agent is adopted in the preparation process to carry out coating modification on the adopted neutron absorbent and gamma absorbent, and the coated and modified functional filler is easier to disperse in a polymer matrix, so that the action probability of neutrons and gamma photons with the functional filler can be improved, and the shielding performance of the obtained shielding material is improved; in addition, the thermal stability and the tensile strength of the composite material are improved to a certain extent by doping the filler.
The invention is realized by the following technical scheme:
a neutron and gamma ray composite shielding material is doped with two surface-modified functional particles as a neutron radiation prevention aid and a gamma radiation prevention aid of the composite shielding material, and 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) and ultrahigh relative molecular weight polyethylene (UHMWPE);
b represents a neutron absorber or neutron absorbers, for example selected from boron carbide (B)4C) Boron oxide (B)2O3) Boric acid (H)3BO3) 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, for example selected from lead (Pb), lead oxide (PbO), gadolinium oxide (Gd)2O3) Tungsten (W), tungsten oxide (WO)3) Bismuth (Bi), bismuth oxide (Bi)2O3) Iron (Fe), iron oxide (Fe)2O3)；
D represents one or more silane coupling agents; it is selected, for example, from gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (. beta. -methoxyethoxy) silane, methylvinyldichlorosilane, methylvinyldimethoxysilane;
a. b, c and d respectively represent mass fraction of A, B, C, D; the range is as follows: a is more than or equal to 30% and less than or equal to 100%, b is more than or equal to 0% and less than or equal to 50%, c is more than or equal to 0% and less than or equal to 50%, d is more than or equal to 0% and less than or equal to 5%, and b + c is more than 0. The material is applied to high-performance neutron shielding with the ambient temperature lower than 100 ℃ and shielding of a neutron and gamma ray mixed field with limited bearing load.
The preparation method of the neutron and gamma ray composite shielding material comprises the following steps:
mixing three powders of modified B or unmodified B, modified C or unmodified C and A; after the mixing is finished, placing the mixed powder into a mold, adding a release agent or release paper, and carrying out hot pressing; the hot pressing procedure is prepressing under the conditions of 0-5Mpa and 120-180 ℃ for 5-20 minutes, pressurizing to 30-100Mpa and keeping constant pressure for 20-180 minutes after the temperature is stabilized to 120-180 ℃, then raising the temperature to 180-300 ℃, pressurizing to 40-100Mpa and keeping constant pressure for 20-180 minutes, and then cooling and removing the mold to obtain the composite shielding material. The mixing is ball milling mixing. The above steps are the hot press molding steps 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 before mixing.
Further, the modified B is prepared by:
(1) weighing the components B and D according to the formula;
(2) dissolving the weighed B in a water-ethanol mixed solution with a 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) dripping the weighed D into the suspension liquid subjected to ultrasonic dispersion in the step (2), then regulating the pH value of the suspension liquid to 3-5 by dripping acetic acid or oxalic acid solution, and stirring the suspension liquid at a constant temperature of 60-120 ℃ for 5-10 hours;
(4) after the above process is finished, separating the waste liquid and the precipitate by centrifuging the suspension, adding an ethanol solution into the precipitate for alcohol washing, and then taking out the precipitate after the alcohol washing and adding ultrapure water for water washing;
preferably, adding an ethanol solution into the precipitate, stirring until the precipitate is uniform, continuing to centrifuge for multiple times until the supernatant is transparent, then taking out the precipitate after the ethanol washing, adding ultrapure water, stirring uniformly, continuing to centrifuge for multiple times until the supernatant is clear;
(5) vacuum drying the cleaned precipitate at 60-120 deg.C for 6-12 hr; or vacuum freeze-drying the washed precipitate for 12-36 hr to obtain modified B. Grinding the B 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.
Further, the modified C is prepared by:
(1) weighing the components C and D according to the formula;
(2) dissolving the weighed C in a water-ethanol mixed solution with a 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) dripping weighed D into the suspension liquid subjected to ultrasonic dispersion in the step (2), then regulating the pH value of the suspension liquid to 3-5 by dripping acetic acid or oxalic acid solution, and stirring the suspension liquid at a constant temperature of 60-120 ℃ for 5-10 hours;
(4) after the above process is finished, separating the waste liquid and the precipitate by centrifuging the suspension, adding an ethanol solution into the precipitate for alcohol washing, and then taking out the precipitate after the alcohol washing and adding ultrapure water for water washing;
preferably, adding an ethanol solution into the precipitate, stirring until the precipitate is uniform, continuing to centrifuge for multiple times until the supernatant is transparent; then taking out the precipitate after the alcohol washing, adding ultrapure water, stirring uniformly, and continuing to centrifugate for multiple times until the supernatant is clear;
(5) vacuum drying the cleaned precipitate at 60-120 deg.C for 6-12 hr; or vacuum freeze-drying the washed precipitate for 12-36 hr to obtain modified C.
The vacuum dried C is milled 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 ambient temperature lower than 100 ℃ and shielding of a neutron and gamma ray mixed field with certain limitation on load.
The invention has the advantages that: the neutron absorber is introduced on the basis of polyethylene, the energy spectrum range of neutron absorption is improved, the gamma absorber is introduced, the shielding capability of the composite material on a mixed radiation field of neutrons and gamma rays is improved, 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 tensile strength of the composite material to a certain extent.
Detailed Description
The following specific examples illustrate the invention in detail. The following examples are only for explaining the present invention, the scope of the present invention shall include the full contents of the claims, and the full contents of the claims of the present invention can be fully realized by those skilled in the art through the following examples.
Example 1:
32g of gadolinium oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic balance and placed in a closed container. Taking out 32g of Gd2O3Putting the powder into a beaker, adding 100ml of absolute ethyl alcohol and 10ml of ultrapure water, uniformly stirring, and putting into an ultrasonic instrument for ultrasonic dispersion, wherein the time is set to 10 minutes. After the ultrasonic treatment is finished, 3.2ml of gamma-methacryloxypropyltrimethoxysilane is dripped into the beaker, then the acetic acid solution is dripped, the PH value of the mixed solution is measured by a PH meter in the dripping process, and the dripping operation is finished until the PH value is 3. The beaker solution was transferred to a three-neck flask in an oil bath pan, and a stirrer was placed and stirred at a constant temperature of 80 ℃ for 10 hours. After the reaction is finished, the mixed solution in the flask is loaded into test tubes in batches, a centrifuge is used for centrifuging for 5 minutes under the condition of 8000r/min, the centrifuged test tube supernatant is poured into a waste liquid barrel, ethanol is added into the test tube filled with the precipitate, the mixture is stirred to be uniform, and then the centrifugation is continuously repeated for 2 to 5 times until the test tube supernatant is transparent; and adding ultrapure water for washing and centrifuging, stirring to be uniform, continuing centrifuging and repeating for 2-5 times until the supernatant of the test tube is clear, and removing the excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was placed in a vacuum drying oven, vacuum-dried at 80 ℃ for 12 hours.
Taking out the dried modified Gd2O3Powder, hereinafter abbreviated as MO-Gd2O3. Grinding in a mortar for 10 minutes to obtain 32g of ground MO-Gd2O3The powder, 32g of boron carbide powder and 256g of high density polyethylene powder were put together into a cylinder of a mixer, and milling balls were added thereto to mix them at 100r/min for 30 minutes. And then transferring the mixed powder into a hot press die, and padding polytetrafluoroethylene release paper for hot pressing. Before hot pressing, the upper heating plate and the lower heating plate of the hot press need to wait for the temperature to reach 120 ℃, after preheating, the heat insulation gloves are worn, the die is placed between the upper heating plate and the lower heating plate, and prepressing is carried out for 5 minutes under the pressure of 2 Mpa. After the pre-pressing is finished, the pressurizing rod is shaken to pressurize to 30Mpa, the temperature is set to be 120 ℃, and the heat preservation and pressure maintaining are carried out for 20 minutes; then, the pressure was increased to 40MPa, the temperature was set at 180 ℃ and the pressure was maintained for 30 minutes.
After the above processes are finished, cooling, pressure relief and demoulding are carried out. Thus obtaining the prepared MO-Gd2O3/B4C/HDPE composite shielding material.
And (3) performing neutron shielding performance test on the prepared material by using a shielding performance test device built by a Cf-252 neutron source, a polyethylene shielding cylinder and a high-sensitivity neutron dosimeter, wherein 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 38.93%, 57.42%, 68.61%, 76.86%, 81.71%, 85.34%, 90.93%, 92.75%, 93.97% and 94.17%.
The gamma shielding performance test device built by a Cs-137 gamma source, a lead chamber and a gamma radiation dosimeter is used for carrying out gamma shielding performance test on the prepared material, and when the thickness of the material is respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured gamma shielding rate is respectively 10.36%, 21.41%, 31.17%, 38.81%, 45.53%, 51.20%, 56.55%, 61.75%, 64.79% and 67.90%.
Example 2:
32g of lead oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are respectively weighed by an electronic balance and placed in a closed container. And taking out 32g of PbO powder, putting the PbO powder into a beaker, adding 100ml of absolute ethyl alcohol and 10ml of ultrapure water, uniformly stirring, and putting the mixture into an ultrasonic instrument for ultrasonic dispersion for 10 minutes. And (3.2) dropwise adding 3.2ml of gamma-methacryloxypropyltrimethoxysilane into the beaker after the ultrasonic treatment is finished, then dropwise adding an 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 value is 3, thus finishing the dropwise adding operation. The beaker solution was transferred to a three-neck flask in an oil bath pan, and a stirrer was placed and stirred at a constant temperature of 80 ℃ for 10 hours. After the reaction is finished, the mixed solution in the flask is loaded into test tubes in batches, a centrifuge is used for centrifuging for 5 minutes under the condition of 8000r/min, the centrifuged test tube supernatant is poured into a waste liquid barrel, ethanol is added into the test tube filled with the precipitate, the mixture is stirred to be uniform, and then the centrifugation is continuously repeated for 2 to 5 times until the test tube supernatant is transparent; and adding ultrapure water for washing and centrifuging, stirring to be uniform, continuing centrifuging and repeating for 2-5 times until the supernatant of the test tube is clear, and removing the excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was placed in a vacuum drying oven and vacuum-dried at 80 ℃ for 12 hours.
The dried modified PbO powder is taken out and is referred to as MO-PbO for short. Grinding for 10 minutes by using a grinding bowl, putting 32g of the grinded MO-PbO powder, 32g of boron carbide powder and 256g of high-density polyethylene powder into a charging barrel of a mixer together, adding grinding balls, and mixing for 30 minutes at the speed of 100 r/min. And then transferring the mixed powder into a hot press die, and padding polytetrafluoroethylene release paper for hot pressing. Before hot pressing, the upper heating plate and the lower heating plate of the hot press need to wait for the temperature to reach 120 ℃, after preheating, the heat insulation gloves are worn, the die is placed between the upper heating plate and the lower heating plate, and prepressing is carried out for 5 minutes under the pressure of 2 Mpa. After the pre-pressing is finished, the pressurizing rod is shaken to pressurize to 30Mpa, the temperature is set to be 120 ℃, and the heat preservation and pressure maintaining are carried out for 20 minutes; then, the pressure was increased to 40MPa, the temperature was set at 180 ℃ and the pressure was maintained for 30 minutes.
After the above processes are finished, cooling, pressure relief and demoulding are carried out. Thus obtaining the prepared MO-PbO/B4C/HDPE composite shielding material.
And (3) performing neutron shielding performance test on the prepared material by using a shielding performance test device built by a Cf-252 neutron source, a polyethylene shielding cylinder and a high-sensitivity neutron dosimeter, wherein when the thicknesses of the materials 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 36.25%, 54.34%, 64.61%, 72.97%, 79.74%, 84.34%, 88.19%, 88.48%, 90.51% and 92.27%.
The gamma shielding performance test device built by a Cs-137 gamma source, a lead chamber and a gamma radiation dosimeter is used for carrying out gamma shielding performance test on the prepared material, and when the thickness of the material is respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured gamma shielding rate is respectively 14.39%, 23.17%, 31.24%, 38.75%, 44.29%, 51.30%, 56.29%, 60.13%, 62.42% and 65.90%.
Example 3:
32g of tungsten powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are respectively weighed by an electronic balance and placed in a closed container. And taking 32g of tungsten powder, putting the tungsten powder into a beaker, adding 100ml of absolute ethyl alcohol and 10ml of ultrapure water, uniformly stirring, and putting the mixture into an ultrasonic instrument for ultrasonic dispersion for 10 minutes. And (3.2) dropwise adding 3.2ml of gamma-methacryloxypropyltrimethoxysilane into the beaker after the ultrasonic treatment is finished, then dropwise adding an 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 value is 3, thus finishing the dropwise adding operation. The beaker solution was transferred to a three-neck flask in an oil bath pan, and a stirrer was placed and stirred at a constant temperature of 80 ℃ for 10 hours. After the reaction is finished, the mixed solution in the flask is loaded into test tubes in batches, a centrifuge is used for centrifuging for 5 minutes under the condition of 8000r/min, the centrifuged test tube supernatant is poured into a waste liquid barrel, ethanol is added into the test tube filled with the precipitate, the mixture is stirred to be uniform, and then the centrifugation is continuously repeated for 2 to 5 times until the test tube supernatant is transparent; and adding ultrapure water for washing and centrifuging, stirring to be uniform, continuing centrifuging and repeating for 2-5 times until the supernatant of the test tube is clear, and removing the excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was placed in a vacuum drying oven and vacuum-dried at 80 ℃ for 12 hours.
The dried modified W is taken out and referred to as MO-W hereinafter. Grinding for 10 minutes by using a grinding bowl, putting 32g of the grinded MO-W powder, 32g of boron carbide powder and 256g of high-density polyethylene powder into a charging barrel of a mixer together, adding grinding balls, and mixing for 30 minutes at the speed of 100 r/min. And then transferring the mixed powder into a hot press die, and padding polytetrafluoroethylene release paper for hot pressing. Before hot pressing, the upper heating plate and the lower heating plate of the hot press need to wait for the temperature to reach 120 ℃, after preheating, the heat insulation gloves are worn, the die is placed between the upper heating plate and the lower heating plate, and prepressing is carried out for 5 minutes under the pressure of 2 Mpa. After the pre-pressing is finished, the pressurizing rod is shaken to pressurize to 30Mpa, the temperature is set to be 120 ℃, and the heat preservation and pressure maintaining are carried out for 20 minutes; then, the pressure was increased to 40MPa, the temperature was set at 180 ℃ and the pressure was maintained for 30 minutes.
After the above processes are finished, cooling, pressure relief and demoulding are carried out. Thus obtaining the prepared MO-W/B4C/HDPE composite shielding material.
And (3) performing neutron shielding performance test on the prepared material by using a shielding performance test device built by a Cf-252 neutron source, a polyethylene shielding cylinder and a high-sensitivity neutron dosimeter, wherein when the thicknesses of the materials 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 built by a Cs-137 gamma source, a lead chamber and a gamma radiation dosimeter is used for carrying out gamma shielding performance test on the prepared material, and when the thickness of the material is respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured gamma shielding rate is respectively 18.64%, 29.83%, 38.29%, 44.48%, 50.39%, 56.14%, 62.80%, 65.89%, 69.42% and 73.37%.
Example 4:
64g of gadolinium oxide powder, 32g of boron carbide powder and 224g of high-density polyethylene powder are weighed by an electronic balance and placed in a closed container. Removing 64g Gd2O3Putting the powder into a beaker, adding 100ml of absolute ethyl alcohol and 10ml of ultrapure water, uniformly stirring, and putting into an ultrasonic instrument for ultrasonic dispersion, wherein the time is set to 10 minutes. And (3.2) dropwise adding 3.2ml of gamma-methacryloxypropyltrimethoxysilane into the beaker after the ultrasonic treatment is finished, then dropwise adding an 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 value is 3, thus finishing the dropwise adding operation. The beaker solution was transferred to a three-neck flask in an oil bath pan, and a stirrer was placed and stirred at a constant temperature of 80 ℃ for 10 hours. After the reaction is finished, the mixed solution in the flask is loaded into test tubes in batches, a centrifuge is used for centrifuging for 5 minutes under the condition of 8000r/min, the centrifuged test tube supernatant is poured into a waste liquid barrel, ethanol is added into the test tube filled with the precipitate, the mixture is stirred to be uniform, and then the centrifugation is continuously repeated for 2 to 5 times until the test tube supernatant is transparent; and adding ultrapure water for washing and centrifuging, stirring to be uniform, continuing centrifuging and repeating for 2-5 times until the supernatant of the test tube is clear, and removing the excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was placed in a vacuum drying oven, vacuum-dried at 80 ℃ for 12 hours.
Taking out the dried modified Gd2O3Powder, hereinafter abbreviated as MO-Gd2O3. Grinding for 10 minutes in a mortar to obtain 64g of ground MO-Gd2O3The powder, 32g of boron carbide powder and 224g of high density polyethylene powder were put togetherPutting the mixture into a cylinder of a mixer, adding grinding balls, and mixing the mixture for 30 minutes at the speed of 100 r/min. And then transferring the mixed powder into a hot press die, and padding polytetrafluoroethylene release paper for hot pressing. Before hot pressing, the upper heating plate and the lower heating plate of the hot press need to wait for the temperature to reach 120 ℃, after preheating, the heat insulation gloves are worn, the die is placed between the upper heating plate and the lower heating plate, and prepressing is carried out for 5 minutes under the pressure of 2 Mpa. After the pre-pressing is finished, the pressurizing rod is shaken to pressurize to 30Mpa, the temperature is set to be 120 ℃, and the heat preservation and pressure maintaining are carried out for 20 minutes; then, the pressure was increased to 40MPa, the temperature was set at 180 ℃ and the pressure was maintained for 30 minutes.
After the above processes are finished, cooling, pressure relief and demoulding are carried out. Thus obtaining the prepared MO-Gd2O3/B4C/HDPE composite shielding material.
The prepared material is subjected to neutron shielding performance test by using a shielding performance test device built by a Cf-252 neutron source, a polyethylene shielding cylinder and a high-sensitivity neutron dosimeter, 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 neutron shielding rates are respectively 38.77%, 56.53%, 62.07%, 72.84%, 79.51%, 84.77%, 87.14%, 89.79%, 91.33% and 92.61%.
The gamma shielding performance test device built by a Cs-137 gamma source, a lead chamber and a gamma radiation dosimeter is used for carrying out gamma shielding performance test on the prepared material, and when the thickness of the material is respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured gamma shielding rate is respectively 13.37%, 24.88%, 34.04%, 41.31%, 48.33%, 54.09%, 59.39%, 64.86%, 68.19% and 72.08%.
Example 5:
32g of gadolinium oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic balance and placed in a closed container. Take out 32g B4And putting the powder C into a beaker, adding 100ml of absolute ethyl alcohol and 10ml of ultrapure water, uniformly stirring, and putting into an ultrasonic instrument for ultrasonic dispersion, wherein the time is set to 10 minutes. After the ultrasonic treatment, 3.2ml of gamma-aminopropyl triethoxy silicon is dripped into the beakerAnd then adding the acetic acid solution dropwise, and measuring the pH value of the mixed solution by using a pH meter during the dropwise adding process until the pH value is 3, thereby finishing the dropwise adding operation. The beaker solution was transferred to a three-neck flask in an oil bath pan, and a stirrer was placed and stirred at a constant temperature of 80 ℃ for 10 hours. After the reaction is finished, the mixed solution in the flask is loaded into test tubes in batches, a centrifuge is used for centrifuging for 5 minutes under the condition of 8000r/min, the centrifuged test tube supernatant is poured into a waste liquid barrel, ethanol is added into the test tube filled with the precipitate, the mixture is stirred to be uniform, and then the centrifugation is continuously repeated for 2 to 5 times until the test tube supernatant is transparent; and adding ultrapure water for washing and centrifuging, stirring to be uniform, continuing centrifuging and repeating for 2-5 times until the supernatant of the test tube is clear, and removing the excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was placed in a vacuum drying oven and vacuum-dried at 80 ℃ for 12 hours.
Taking out the dried modification B4C powder, hereinafter referred to as MO-B4C. The modified powder was ground in a mortar for 10 minutes, and 32g of the ground MO-B powder was added4C powder, 32gGd2O3The powder was put into a cylinder of a blender together with 256g of high density polyethylene powder, and milling balls were added thereto and mixed at 100r/min for 30 minutes. And then transferring the mixed powder into a hot press die, and padding polytetrafluoroethylene release paper for hot pressing. Before hot pressing, the upper heating plate and the lower heating plate of the hot press need to wait for the temperature to reach 120 ℃, after preheating, the heat insulation gloves are worn, the die is placed between the upper heating plate and the lower heating plate, and prepressing is carried out for 5 minutes under the pressure of 2 Mpa. After the pre-pressing is finished, the pressurizing rod is shaken to pressurize to 30Mpa, the temperature is set to be 120 ℃, and the heat preservation and pressure maintaining are carried out for 20 minutes; then, the pressure was increased to 40MPa, the temperature was set at 180 ℃ and the pressure was maintained for 30 minutes.
After the above processes are finished, cooling, pressure relief and demoulding are carried out. Thus obtaining the prepared Gd2O3/MO-B4C/HDPE composite shielding material.
And (3) performing neutron shielding performance test on the prepared material by using a shielding performance test device built by a Cf-252 neutron source, a polyethylene shielding cylinder and a high-sensitivity neutron dosimeter, wherein when the thicknesses of the materials 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 built by the Cs-137 gamma source, the lead chamber and the gamma radiation dosimeter is used for carrying out gamma shielding performance test on the prepared material, and when the thickness of the material is respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured gamma shielding rate is respectively 10.80%, 19.29%, 28.57%, 35.83%, 41.58%, 49.28%, 52.14%, 57.89%, 61.85% and 64.99%.
Example 6:
weighing 32g of gadolinium oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder by using an electronic balance, and mixing 32g of Gd2O3Powder, 32g B4The C powder and 256g of high density polyethylene powder were put together into a cylinder of a mixer, and milling balls were added thereto to mix them at 100r/min for 30 minutes. And then transferring the mixed powder into a hot press die, and padding polytetrafluoroethylene release paper for hot pressing. Before hot pressing, the upper heating plate and the lower heating plate of the hot press need to wait for the temperature to reach 120 ℃, after preheating, the heat insulation gloves are worn, the die is placed between the upper heating plate and the lower heating plate, and prepressing is carried out for 5 minutes under the pressure of 2 Mpa. After the pre-pressing is finished, the pressurizing rod is shaken to pressurize to 30Mpa, the temperature is set to be 120 ℃, and the heat preservation and pressure maintaining are carried out for 20 minutes; then, the pressure was increased to 40MPa, the temperature was set at 180 ℃ and the pressure was maintained for 30 minutes.
After the above processes are finished, cooling, pressure relief and demoulding are carried out. Thus obtaining the prepared Gd2O3/B4C/HDPE composite shielding material.
And (3) performing neutron shielding performance test on the prepared material by using a shielding performance test device built by a Cf-252 neutron source, a polyethylene shielding cylinder and a high-sensitivity neutron dosimeter, wherein 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 34.72%, 57.39%, 65.46%, 74.28%, 76.42%, 82.11%, 84.87%, 88.02%, 89.77% and 90.02%.
The gamma shielding performance test device built by a Cs-137 gamma source, a lead chamber and a gamma radiation dosimeter is used for carrying out gamma shielding performance test on the prepared material, and when the thickness of the material is respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured gamma shielding rate is respectively 10.83%, 19.94%, 28.53%, 35.19%, 41.62%, 49.77%, 52.38%, 57.24%, 61.22% and 64.13%.
Example 7:
32g of gadolinium oxide powder, 32g of boron carbide powder and 256g of high-density polyethylene powder are weighed by an electronic balance and placed in a closed container. Taking out 32g of Gd2O3Putting the powder into a beaker, adding 100ml of absolute ethyl alcohol and 10ml of ultrapure water, uniformly stirring, and putting into an ultrasonic instrument for ultrasonic dispersion, wherein the time is set to 10 minutes. And (3.2) dropwise adding 3.2ml of gamma-methacryloxypropyltrimethoxysilane into the beaker after the ultrasonic treatment is finished, then dropwise adding an 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 value is 3, thus finishing the dropwise adding operation. The beaker solution was transferred to a three-neck flask in an oil bath pan, and a stirrer was placed and stirred at a constant temperature of 80 ℃ for 10 hours. After the reaction is finished, the mixed solution in the flask is loaded into test tubes in batches, a centrifuge is used for centrifuging for 5 minutes under the condition of 8000r/min, the centrifuged test tube supernatant is poured into a waste liquid barrel, ethanol is added into the test tube filled with the precipitate, the mixture is stirred to be uniform, and then the centrifugation is continuously repeated for 2 to 5 times until the test tube supernatant is transparent; and adding ultrapure water for washing and centrifuging, stirring to be uniform, continuing centrifuging and repeating for 2-5 times until the supernatant of the test tube is clear, and removing the excessive coupling agent, acetic acid and other impurities in the precipitate. The washed precipitate was placed in a vacuum drying oven and vacuum-dried at 80 ℃ for 12 hours.
Adopt the above steps to B4The same treatment is carried out on the powder C to obtain modified B4And C, powder.
Taking out the dried modified Gd2O3Powder and modification B4C powder, hereinafter abbreviated toMO-Gd2O3And MO-B4C. The two modified powders were ground in a mortar for 10 minutes, and 32g of the ground MO-Gd2O3Powder, 32g of milled MO-B4The C powder and 256g of high density polyethylene powder were put together into a cylinder of a mixer, and milling balls were added thereto to mix them at 100r/min for 30 minutes. And then transferring the mixed powder into a hot press die, and padding polytetrafluoroethylene release paper for hot pressing. Before hot pressing, the upper heating plate and the lower heating plate of the hot press need to wait for the temperature to reach 120 ℃, after preheating, the heat insulation gloves are worn, the die is placed between the upper heating plate and the lower heating plate, and prepressing is carried out for 5 minutes under the pressure of 2 Mpa. After the pre-pressing is finished, the pressurizing rod is shaken to pressurize to 30Mpa, the temperature is set to be 120 ℃, and the heat preservation and pressure maintaining are carried out for 20 minutes; then, the pressure was increased to 40MPa, the temperature was set at 180 ℃ and the pressure was maintained for 30 minutes.
After the above processes are finished, cooling, pressure relief and demoulding are carried out. Thus obtaining the prepared MO-Gd2O3/MO-B4C/HDPE composite shielding material.
And (3) performing neutron shielding performance test on the prepared material by using a shielding performance test device built by a Cf-252 neutron source, a polyethylene shielding cylinder and a high-sensitivity neutron dosimeter, wherein 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 built by a Cs-137 gamma source, a lead chamber and a gamma radiation dosimeter is used for carrying out gamma shielding performance test on the prepared material, and when the thickness of the material is respectively 1.5cm, 3cm, 4.5cm, 6cm, 7.5cm, 9cm, 10.5cm, 12cm, 13.5cm and 15cm, the measured gamma shielding rate is respectively 12.70%, 21.87%, 30.64%, 37.63%, 43.74%, 51.60%, 54.69%, 59.75%, 65.26% and 67.93%.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and the preferred embodiments are not exhaustive and do not limit the invention to the precise embodiments described. Various modifications and improvements of the technical solution of the present invention may be made by those skilled in the art without departing from the spirit of the present invention, and the technical solution of the present invention is to be covered by the protection scope defined by the claims.
Claims (10)
1. A neutron and gamma ray composite shielding material is doped with two surface-modified functional particles as a neutron absorber and a gamma absorber of the composite shielding material, and is characterized in that the formula of the composite shielding material is as follows:
aA+bB+cC+dD
in the general formula:
a represents one or more of High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE) and ultrahigh relative molecular weight polyethylene (UHMWPE);
b represents a neutron absorber or neutron absorbers, for example selected from boron carbide (B)4C) Boron oxide (B)2O3) Boric acid (H)3BO3) 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, for example selected from lead (Pb), lead oxide (PbO), gadolinium oxide (Gd)2O3) Tungsten (W), tungsten oxide (WO)3) Bismuth (Bi), bismuth oxide (Bi)2O3) Iron (Fe), iron oxide (Fe)2O3)；
D represents one or more silane coupling agents, for example selected from gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (. beta. -methoxyethoxy) silane, methylvinyldichlorosilane, methylvinyldimethoxysilane.
a. b, c and d respectively represent mass fraction of A, B, C, D; the range is as follows: a is more than or equal to 30% and less than or equal to 100%, b is more than or equal to 0% and less than or equal to 50%, c is more than or equal to 0% and less than or equal to 50%, d is more than or equal to 0% and less than or equal to 5%, and b + c is more than 0.
2. The neutron and gamma ray composite shielding material of claim 1, wherein the material is applied to high performance neutron shielding with ambient temperature below 100 ℃ and shielding of a neutron and gamma ray mixed field with limited bearing load.
3. The method for preparing the neutron and gamma ray composite shielding material according to claim 1, which comprises the following steps:
mixing three powders of modified B or unmodified B, modified C or unmodified C and A; after the mixing is finished, placing the mixed powder into a mold, adding a release agent or release paper, and carrying out hot pressing; the hot pressing procedure is prepressing under the conditions of 0-5Mpa and 120-180 ℃ for 5-20 minutes, pressurizing to 30-100Mpa and keeping constant pressure for 20-180 minutes after the temperature is stabilized to 120-180 ℃, then raising the temperature to 180-300 ℃, pressurizing to 40-100Mpa and keeping constant pressure for 20-180 minutes, and then cooling and removing the mold to obtain the composite shielding material.
4. The method of claim 3, wherein the modified B is milled for 5 minutes to half an hour prior to mixing.
5. The method of claim 3, wherein the modified C is milled for 5 minutes to half an hour prior to mixing.
6. The method of claim 3, wherein the mixing is ball milling.
7. The method of claim 3, wherein the modified B is prepared by:
(1) weighing the components B and D according to the formula of claim 1;
(2) dissolving the weighed B in a water-ethanol mixed solution with a 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) dripping the weighed D into the suspension liquid subjected to ultrasonic dispersion in the step (2), then regulating the pH value of the suspension liquid to 3-5 by dripping acetic acid or oxalic acid solution, and stirring the suspension liquid at a constant temperature of 60-120 ℃ for 5-10 hours;
(4) after the above process is finished, separating the waste liquid and the precipitate by centrifuging the suspension, adding an ethanol solution into the precipitate for alcohol washing, and then taking out the precipitate after the alcohol washing and adding ultrapure water for water washing;
preferably, adding an ethanol solution into the precipitate, stirring until the precipitate is uniform, continuing to centrifuge for multiple times until the supernatant is transparent; then taking out the precipitate after the alcohol washing, adding ultrapure water, stirring uniformly, and continuing to centrifugate for multiple times until the supernatant is clear;
(5) vacuum drying the cleaned precipitate at 60-120 deg.C for 6-12 hr; or vacuum freeze-drying the washed precipitate for 12-36 hr to obtain modified B.
8. The method of claim 3, wherein the modified C is prepared by:
(1) weighing the components C and D according to the formula of claim 1;
(2) dissolving the weighed C in a water-ethanol mixed solution with a 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) dripping the weighed D into the suspension liquid subjected to ultrasonic dispersion in the step (2), then regulating the pH value of the suspension liquid to 3-5 by dripping acetic acid or oxalic acid solution, and stirring the suspension liquid at a constant temperature of 60-120 ℃ for 5-10 hours;
(4) after the above process is finished, separating the waste liquid and the precipitate by centrifuging the suspension, adding an ethanol solution into the precipitate for alcohol washing, and then taking out the precipitate after the alcohol washing and adding ultrapure water for water washing;
preferably, adding an ethanol solution into the precipitate, stirring until the precipitate is uniform, continuing to centrifuge for multiple times until the supernatant is transparent, then taking out the precipitate after the ethanol washing, adding ultrapure water, stirring uniformly, continuing to centrifuge for multiple times until the supernatant is clear;
(5) vacuum drying the cleaned precipitate at 60-120 deg.C for 6-12 hr; or vacuum freeze-drying the washed precipitate for 12-36 hr to obtain modified C.
9. The method according to claim 7 or 8, wherein the steps (2) (3) (4) (5) are a step of coating-modifying the functional filler with a silane coupling agent.
10. The method of claim 3, wherein said step is a step of hot press forming the composite shielding material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110522142.4A CN113201180B (en) | 2021-05-13 | 2021-05-13 | Neutron and gamma ray composite shielding material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110522142.4A CN113201180B (en) | 2021-05-13 | 2021-05-13 | Neutron and gamma ray composite shielding material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113201180A true CN113201180A (en) | 2021-08-03 |
| CN113201180B CN113201180B (en) | 2024-03-01 |
Family
ID=77031007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110522142.4A Active CN113201180B (en) | 2021-05-13 | 2021-05-13 | Neutron and gamma ray composite shielding material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113201180B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835492A (en) * | 2022-05-18 | 2022-08-02 | 厦门稀土材料研究所 | Rare earth-based zirconium-hafnium composite ceramic material and preparation method and application thereof |
| CN115572162A (en) * | 2022-04-29 | 2023-01-06 | 厦门稀土材料研究所 | Rare earth medium-high entropy hafnate ceramic material for controlling reactor neutron |
| CN115785585A (en) * | 2023-02-09 | 2023-03-14 | 中星(广州)纳米材料有限公司 | Neutron and gamma ray shielding material, preparation method and application |
| WO2024019679A1 (en) * | 2022-07-20 | 2024-01-25 | Karadeni̇z Tekni̇k Uni̇versi̇tesi̇ Teknoloji̇ Transferi̇ Uygulama Ve Arasti̇rma Merkezi̇ | A neutron absorber material with boron minerals and bismutoxide additive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409124A (en) * | 2014-11-26 | 2015-03-11 | 北京富迪创业科技有限公司 | High-filling composite shielding material for radiation mixing fields and preparation method of high-filling composite shielding material |
| CN108912463A (en) * | 2018-08-06 | 2018-11-30 | 中国科学院合肥物质科学研究院 | A kind of gadolinium Base Metal organic backbone composite shielding material and preparation method |
| CN108948463A (en) * | 2018-01-11 | 2018-12-07 | 天津天颐科苑科技有限公司 | A kind of X, gamma Rays and neutron radiation protection material and preparation method thereof |
| CN109575606A (en) * | 2019-01-16 | 2019-04-05 | 东莞理工学院 | A kind of neutron shielding material and preparation method thereof |
-
2021
- 2021-05-13 CN CN202110522142.4A patent/CN113201180B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409124A (en) * | 2014-11-26 | 2015-03-11 | 北京富迪创业科技有限公司 | High-filling composite shielding material for radiation mixing fields and preparation method of high-filling composite shielding material |
| CN108948463A (en) * | 2018-01-11 | 2018-12-07 | 天津天颐科苑科技有限公司 | A kind of X, gamma Rays and neutron radiation protection material and preparation method thereof |
| CN108912463A (en) * | 2018-08-06 | 2018-11-30 | 中国科学院合肥物质科学研究院 | A kind of gadolinium Base Metal organic backbone composite shielding material and preparation method |
| CN109575606A (en) * | 2019-01-16 | 2019-04-05 | 东莞理工学院 | A kind of neutron shielding material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572162A (en) * | 2022-04-29 | 2023-01-06 | 厦门稀土材料研究所 | Rare earth medium-high entropy hafnate ceramic material for controlling reactor neutron |
| CN114835492A (en) * | 2022-05-18 | 2022-08-02 | 厦门稀土材料研究所 | Rare earth-based zirconium-hafnium composite ceramic material and preparation method and application thereof |
| WO2024019679A1 (en) * | 2022-07-20 | 2024-01-25 | Karadeni̇z Tekni̇k Uni̇versi̇tesi̇ Teknoloji̇ Transferi̇ Uygulama Ve Arasti̇rma Merkezi̇ | A neutron absorber material with boron minerals and bismutoxide additive |
| CN115785585A (en) * | 2023-02-09 | 2023-03-14 | 中星(广州)纳米材料有限公司 | Neutron and gamma ray shielding material, preparation method and application |
| CN115785585B (en) * | 2023-02-09 | 2023-05-02 | 中星(广州)纳米材料有限公司 | Neutron and gamma ray shielding material, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113201180B (en) | 2024-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113201180B (en) | Neutron and gamma ray composite shielding material and preparation method thereof | |
| EP1600984B1 (en) | Cask, composition for neutron shielding body, and method of manufacturing the neutron shielding body | |
| CN109575606A (en) | A kind of neutron shielding material and preparation method thereof | |
| CN110619969B (en) | Radiation shielding container and preparation method thereof | |
| KR20100047510A (en) | Radiation shielding members including nano-particles as a radiation shielding materials and preparation method thereof | |
| KR101589692B1 (en) | Radiation shielding meterial including tungsten or boron nano-particles and preparation method thereof | |
| CN104277173B (en) | Polyacrylic acid metal salt/boron oxide material and its preparation method and application | |
| Jing et al. | Research progress of rare earth composite shielding materials | |
| Cinan et al. | Gamma irradiation, thermal conductivity, and phase change tests of the cement‐hyperbranched poly amino‐ester‐block‐poly cabrolactone‐polyurathane plaster‐lead oxide and arsenic oxide composite for development of radiation shielding material | |
| CN110415851B (en) | Cement-based neutron shielding material and preparation method thereof | |
| CN108912463B (en) | Gadolinium-based metal organic framework composite shielding material and preparation method thereof | |
| CN101486809B (en) | Preparation of rare-earth oxide / natural rubber composite material for X radiation protection | |
| CN112574533A (en) | High-temperature-resistant borosilicate resin neutron shielding material and preparation process thereof | |
| CN112812498A (en) | Preparation method of functionalized carbon nanotube modified resin-based composite radiation protection material | |
| Tashlykov et al. | An extensive experimental study on the role of micro-size pozzolana in enhancing the gamma-ray shielding properties of high-density polyethylene | |
| Salawu et al. | Assessment of radiation shielding properties of polymer-lead (II) oxide composites | |
| JP2003255081A (en) | Radiation shield material composition | |
| CN108257702B (en) | Hydrogen-free neutron shielding material of a kind of high intensity high boron content and preparation method thereof | |
| JP2003050295A (en) | Composition for neutron shielding material, shielding material and vessel | |
| EP4269366A1 (en) | Inorganic composition and fibers and flakes thereof | |
| CN111825911B (en) | Polymer composite material for space neutron shielding and preparation method thereof | |
| CN113956846B (en) | Rare earth oxide nanoparticle doped Mxene material for space charged particle radiation protection, composite coating and preparation method | |
| KR20150111886A (en) | Composite for protecting of radiation and manufacturing method thereof | |
| KR100889286B1 (en) | Polyethylene Shielding Material Containing Boron And Lead And Method For Preparing The Same | |
| CN115304982B (en) | Packaging shielding coating for spaceborne integrated circuit and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |