WO2018038566A1 - Composition de protection contre le rayonnement comprenant des nanoparticules de bore, et son procédé de fabrication - Google Patents

Composition de protection contre le rayonnement comprenant des nanoparticules de bore, et son procédé de fabrication Download PDF

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Publication number
WO2018038566A1
WO2018038566A1 PCT/KR2017/009290 KR2017009290W WO2018038566A1 WO 2018038566 A1 WO2018038566 A1 WO 2018038566A1 KR 2017009290 W KR2017009290 W KR 2017009290W WO 2018038566 A1 WO2018038566 A1 WO 2018038566A1
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WIPO (PCT)
Prior art keywords
nanoparticles
group
radiation shielding
boron
shielding composition
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PCT/KR2017/009290
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English (en)
Korean (ko)
Inventor
조원일
Original Assignee
주식회사 쇼나노
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from KR1020170106927A external-priority patent/KR101910970B1/ko
Application filed by 주식회사 쇼나노 filed Critical 주식회사 쇼나노
Publication of WO2018038566A1 publication Critical patent/WO2018038566A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a radioactive shielding composition comprising boron nanoparticles and a method for producing the same, and more particularly to a radioactive shielding composition comprising a boron particle having a hydroxyl group, an alkoxy group or a carboxyl group bonded to a surface thereof, and a method for producing the same. It is about.
  • Nanotechnology is a core technology of 21st century science and technology, which is not only used to induce the technological innovation by combining with the traditional manufacturing industry, but also as a foundation technology that can further enhance future core strategic projects by integrating with advanced technologies such as IT, BT, CT, etc. It is recognized as the next generation growth engine.
  • Methods of manufacturing nanomaterials applied to such advanced technologies include laser heating, liquid phase synthesis, solid phase synthesis, and the like.
  • Liquid phase synthesis is basically a batch process, and since contact with various solvents and foreign substances is inevitably followed, impurities are difficult to synthesize high-purity nanoparticles, and in the case of laser heating, There is no contact at all, there is an advantage that can be produced nanoparticles continuously.
  • the nanoparticle synthesis apparatus using the CO2 laser pyrolysis method for supplying a raw material gas such as a laser irradiation unit, a reaction chamber, a collecting unit and a vacuum pump and monosilane into the reaction chamber. It is composed of an injection portion provided with a carrier gas supply nozzle for supplying a carrier gas, such as source gas supply nozzle and helium (He) gas.
  • a carrier gas such as source gas supply nozzle and helium (He) gas.
  • the laser beam irradiated from the laser irradiation unit is irradiated into the reaction chamber through the reflecting mirror and the lens, at this time monosilane injected into the reaction chamber through the source gas supply nozzle of the injection unit, etc.
  • the same source gas is decomposed by the heat of the laser beam, nanoparticles are formed, and the nanoparticles uniformly grown in the reaction chamber form negative pressure in the reaction chamber by a vacuum pump, thereby moving the nanoparticles out of the reaction chamber.
  • a method for synthesizing nanoparticles by irradiating laser to a source gas such as a metal oxide compound, and the synthesis method for producing silicon / germanium nanoparticles by laser pyrolysis is known, pulsed in tetramethylgermanium gas Irradiation of the laser, including the step of photolysis
  • the method for producing germanium nanoparticles is known that the yield of germanium nanoparticles is 70 to 80%, germanium antimony telluride-based, germanium bismuth telluride-based, germanium antimony selenide Germanium Bismuth Selenide, Indium Antimony Telluride, Phosphorus Bismuth telluride, indium antimony selenide, indium bismuth selenide, indium antimony germanide, gallium antimony
  • the method of manufacturing nanoparticles by the laser heating method has the advantage of manufacturing high purity nanoparticles, but the production yield of nanoparticles is low, and the environment is damaged when raw gas, which is unreacted toxic gas, is discarded as a by-product. In addition, there is a problem in that the system becomes complicated and expensive when the raw material gas that is disposed of is recovered and not reused.
  • Patent Document 0001 Korean Patent Publication No. 10-2013-0130284
  • Patent Document 0002 Korean Patent Registration No. 10-1363478
  • the present invention is to solve the above problems of the prior art, an object of the present invention is to provide a radioactive shielding composition which is economically advantageous because of excellent radiation shielding performance and a simple manufacturing process.
  • the present invention provides a radioactive shielding boron nanoparticles having a hydroxyl group, an alkoxy group or a carboxyl group bonded to the surface thereof.
  • the particle size of the boron nanoparticles may be boron nanoparticles having a hydroxyl group, an alkoxy group or a carboxyl group of 5 to 400 nm bonded to the surface, and the radiation shielding composition may further include a binder resin.
  • boron nanoparticle refers to a particle having a surface of hydride
  • surface-modified boron nanoparticle is a surface of a hydroxyl group, an alkoxy group, boron nano having a carboxyl group bonded to the surface It can be understood as the concept of particles.
  • the surface-modified boron nanoparticles prepared by reacting the surface with water, ethanol, polyol, and stearic acid will be described as representative examples, but the nanoparticles constituting the radiation shielding composition according to the embodiment of the present invention are limited thereto. It doesn't work.
  • the wavelength of the CO 2 laser is matched to the absorption cross-sectional area of the diborane source gas in the mixed gas, so that energy is easily absorbed by the raw material molecules, thereby divorcing by intense vibration of the molecules. Break the BH bond of the diborane molecule and break it down into radical form, respectively.
  • the silicon radicals generated as described above develop into boron nanoparticle nuclei by homogeneous nucleation, and grow gradually by binding to surrounding boron radicals. Therefore, the surrounding environment of boron radicals, the residence time in which the boron nanoparticle nucleus stays in the reaction zone, and the like are important factors controlling the size and characteristics of the boron nanoparticles.
  • the laser is generated and irradiated by a CO 2 laser generator, and is irradiated in the form of a line beam of continuous waves having a wavelength of 10.6 ⁇ m.
  • the CO 2 laser generator preferably uses a maximum output of 50 to 60 W. However, depending on the size of the nanoparticle manufacturing apparatus or the amount of nanoparticles to be produced, a maximum output of about 6,000W laser can be used.
  • the reaction chamber may have an internal pressure of 100 to 500 torr, but is not limited thereto. If the internal pressure of the reaction chamber is less than 100torr, raw material gas decomposition may not be performed smoothly, and thus the production yield of nanoparticles may be lowered.
  • Diborane gas may have an explosive reaction when it receives energy from the outside and is excited.
  • the reaction process is shown in Scheme 1 below.
  • the boron nanoparticles may have a size of 5 to 400 nm, preferably 10 to 100 nm, but are not limited thereto. If the boron nanoparticles are less than 5 nm in size, nanometer-based particles may not be easily manufactured. If the boron nanoparticles are larger than 400 nm, the surface area of the particles may be reduced, resulting in a problem of deterioration.
  • R may be any one selected from the group consisting of hydrogen, alkyl group, aminoketyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group and aminoallyl group.
  • the material used for surface modification of the boron nanoparticles may be water, alcohol, fatty acid, preferably water, methanol, ethanol, polyol, stearic acid, but is not limited thereto.
  • Radiation generally consists of alpha rays, beta rays and gamma rays.
  • the boron nanoparticles are materials capable of shielding gamma rays, and are generally compounded in a binder resin through a biaxial extruder and manufactured in a sheet form to be used as a radiation shielding material.
  • the binder resin is low density polyethylene (LDPE), high density polyethylene (HDPE), polyvinyl alcohol (polyvinylalcohol, PVA), PET (polyethylene terephthalate), EPM (copolymer of ethylene and propylene), polyurethane (polyurethane) ), Polyurea, silicone resin, epoxy resin, acrylic resin, polyphenylene sulfide (PPS), polyether ether ketone (PEEK) and mixtures of two or more thereof It may be one selected from the group consisting of, preferably silicone resin, but is not limited thereto.
  • the radiation shielding composition may be in the form of liquid, gel, and solid, and may be processed into a product such as fiber, film, sheet, and sealant, but is not limited thereto.
  • the silicone resin has excellent resilience, chemical resistance, heat resistance, flame retardancy, weather resistance, chemical resistance, hot water resistance, oil resistance, insulation, non-toxicity, strength, low temperature elasticity, and when the composition containing the silicone resin is used as a radiation shielding material. Since the tensile strength, elongation, friction fastness and the like is excellent, there is an advantage that the coated portion is not peeled off arbitrarily. In addition, the silicone resin is not only harmful to the human body, but also has a long life of the shielding material.
  • the silicone resin may be, for example, one selected from the group consisting of dimethylsiloxane, polydimethylsiloxane, polyether modified polydimethylsiloxane, oligosiloxane, and mixtures of two or more thereof.
  • the radiation shielding composition may further include one selected from the group consisting of alkaline earth metal compounds, tourmalines, metals, transition metals, lanthanides, actinides, and mixtures of two or more thereof, and more particularly, tin (Sn). ), Antimony (Sb), tellurium (Te), iodine (I), xenon (Xe), cesium (Cs), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd) ), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Tolium (Tm), Ytterbium (Yb) ), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), O
  • the radiation shielding composition according to an embodiment may further increase the shielding efficiency of beta rays, alpha rays, as well as gamma rays by further comprising one of the metals or a mixture of metals listed above in the boron nanoparticles.
  • the boron nanoparticles may be included in the form of a diluted solution and powder in a concentration of 5 to 50,000 ppm, and the content of the solution and powder may be 1 to 20 parts by weight based on 100 parts by weight of the binder resin. Can be.
  • preparing a boron surface-modified nanoparticles preparing a boron surface-modified nanoparticles; And mixing the boron nanoparticles, a liquid binder resin, and a resin cured material.
  • Radioactive shielding composition according to an aspect of the present invention, by adjusting the particle size of the boron nanoparticles to a certain range, by modifying the surface of the boron nanoparticles and including a binder resin, the radiation shielding performance is excellent, the manufacturing process is simple, productivity, It is advantageous in terms of economics.
  • surface modification means that a functional group is bonded to the surface of a particle.
  • Diborane gas (B 2 H 6 ), catalyst gas sulfur hexafluoride (SF6) and nitrogen are mixed and injected into the reaction chamber to irradiate a CO 2 laser beam.
  • the sulfur hexafluoride (SF6) gas is a catalyst. It acts as a gas, and energy absorbed at a wavelength of 10.6 ⁇ m is efficiently transferred, and the boron nanoparticles (B-NPs) are generated by breaking the BH bond of diborane gas well.
  • the catalyst gas (sulfur hexafluoride, SF6) is adjusted to the range of less than 10% of the total volume.
  • the carrier gas nitrogen is not more than 400 parts by volume compared to the diborane gas source gas. The flow rate of gas is in sccm.
  • Process pressure inside the reaction chamber is prepared by setting in the range of 100 ⁇ 400 Torr. In this range, boron nanoparticles (B-NPs) having a size of 5 to 400 nm are prepared.
  • Example 1-1 Example 1-2
  • Example 1-3 Example 1-4
  • Example 1-5 Raw material gas (sccm) 300 500 700 1000 1500 Catalyst gas (sccm) 15 36 60 80 105 Carrier gas (sccm) 400 400 400 500 500 Process pressure (Torr) 350-200 350-200 250-100 250-100 200-100 Particle Size (nm) 20-30 20-30 20-30 20-30 20-30 20-30
  • Example 1 The boron nanoparticles prepared in Example 1 were dissolved in dichloromethane (25 ml) solution of 100 mg of water, ethanol, polyol or stearic acid according to Scheme 2 to react hydroxy, alkoxy and carboxyl groups on the particle surface. Nanoparticles (Examples 2-1 to 2-4) were prepared.
  • R may be any one selected from the group consisting of hydrogen, alkyl group, aminoketyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group and aminoallyl group.
  • Radioactive shielding composition comprising a radioactive shielding boron nanoparticles prepared in Example 2 (Examples 2-1 to 2-4) (95 to 99.5 wt% mononuclear silicone resin, 0.5 to 5 wt% nanoparticles) After a constant 100mm thickness was applied to the substrate and semi-dried, it was placed on the belt of the drying unit and dried at room temperature for about 24 hours. Cooling air is blown to the completely dried substrate by using a blower to completely cure it, and then peeled off the substrate to remove the radioactive shielding material having a concentration of boron nanoparticles of 0.5, 3.0, and 5.0% by weight (Examples 3-1-1 to 3- 4-3).
  • Radioactive shielding composition (B2O3 nanoparticles (5%) comprising a comparative example (B 2 O 3 particles purchased from Aldrich) and the radioactive shielding boron nanoparticles prepared in Example 2 (Examples 2-1 to 2-4) ), Boron nanoparticles (0.5, 3.0, 5.0 wt%) of HDPE and chips compounded in a twin screw extruder at 170 o C) were fabricated 10 mm thick 300mm x 300mm sheet through several hot presses (comparative example, carried out) Examples 4-1-1 to 4-4-3) were used to analyze radiation (gamma) shielding performance at Cf-252 and Am / Be-241.
  • Tables 3 and 4 below show the results of radiological shielding analysis for Comparative Examples and Examples 3-1-1 to 3-4-3 and Examples 4-1-1 to 4-4-3. Radiation Quality in Table 1 is Cf-252 and Am / Be-241, respectively.
  • Example 3-1-1 ((300x300x10 (T) mm 3 ) 28.9 24.6
  • Example 3-1-2 ((300x300x10 (T) mm 3 ) Over 99 Over 99
  • Example 3-1-3 ((300x300x10 (T) mm 3 ) Over 99 Over 99
  • Example 3-2-1 ((300x300x10 (T) mm 3 ) 30.2 26.3
  • Example 3-2-2 ((300x300x10 (T) mm 3 ) Over 99 Over 99
  • Example 3-2-3 ((300x300x10 (T) mm 3 ) Over 99 Over 99
  • Example 3-3-1 ((300x300x10 (T) mm 3 ) 30.9 27.4
  • Example 3-3-2 ((300x300x10 (T) mm 3 ) Over 99 Over 99
  • Example 3-3-3 ((300x300x10 (T) mm 3 ) Over 99 Over 99
  • Example 3-4-1 ((300x300x300x300x)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un mode de réalisation de la présente invention concerne une composition de protection contre le rayonnement comprenant des nanoparticules de bore pour la protection contre le rayonnement, qui comprennent un groupe hydroxyle, un groupe alcoxy ou un groupe carboxyle se liant à leurs surfaces.
PCT/KR2017/009290 2016-08-24 2017-08-24 Composition de protection contre le rayonnement comprenant des nanoparticules de bore, et son procédé de fabrication WO2018038566A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160107746 2016-08-24
KR10-2016-0107746 2016-08-24
KR1020170106927A KR101910970B1 (ko) 2016-08-24 2017-08-23 보론 나노입자를 포함하는 방사능 차폐재 조성물 및 이의 제조 방법
KR10-2017-0106927 2017-08-23

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050211930A1 (en) * 1998-12-07 2005-09-29 Meridian Research And Development Radiation detectable and protective articles
US20090078891A1 (en) * 2005-02-23 2009-03-26 Kabushiki Kaisha Toshiba Radiation shielding sheet
US20130048887A1 (en) * 2011-08-22 2013-02-28 Steven M. Yoder Radiation Barrier Panel
US20130161564A1 (en) * 2011-12-22 2013-06-27 International Scientific Technologies, Inc. NanoStructured Additives to High-Performance Polymers for Use in Radiation Shielding, Protection Against Atomic Oxygen and in Structural Applications
WO2016036088A1 (fr) * 2014-09-05 2016-03-10 한국엔지니어링플라스틱 주식회사 Composition de résine acétal

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050211930A1 (en) * 1998-12-07 2005-09-29 Meridian Research And Development Radiation detectable and protective articles
US20090078891A1 (en) * 2005-02-23 2009-03-26 Kabushiki Kaisha Toshiba Radiation shielding sheet
US20130048887A1 (en) * 2011-08-22 2013-02-28 Steven M. Yoder Radiation Barrier Panel
US20130161564A1 (en) * 2011-12-22 2013-06-27 International Scientific Technologies, Inc. NanoStructured Additives to High-Performance Polymers for Use in Radiation Shielding, Protection Against Atomic Oxygen and in Structural Applications
WO2016036088A1 (fr) * 2014-09-05 2016-03-10 한국엔지니어링플라스틱 주식회사 Composition de résine acétal

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