EP3436546A1 - Kunststoffszintillator, detektor, zugehöriges herstellungsverfahren und szintillationsmessverfahren - Google Patents
Kunststoffszintillator, detektor, zugehöriges herstellungsverfahren und szintillationsmessverfahrenInfo
- Publication number
- EP3436546A1 EP3436546A1 EP17718390.2A EP17718390A EP3436546A1 EP 3436546 A1 EP3436546 A1 EP 3436546A1 EP 17718390 A EP17718390 A EP 17718390A EP 3436546 A1 EP3436546 A1 EP 3436546A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluorophore
- plastic
- scintillation
- gadolinium
- polymeric matrix
- 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.)
- Withdrawn
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 104
- 229920003023 plastic Polymers 0.000 title claims abstract description 104
- 238000005259 measurement Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 81
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- SAXNQWFLHXTRDI-UHFFFAOYSA-N 9-(2-ethylhexyl)carbazole Chemical compound C1=CC=C2N(CC(CC)CCCC)C3=CC=CC=C3C2=C1 SAXNQWFLHXTRDI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 230000005855 radiation Effects 0.000 claims description 18
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 14
- 238000001514 detection method Methods 0.000 claims description 14
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 239000012857 radioactive material Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 10
- 230000002745 absorbent Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 230000005865 ionizing radiation Effects 0.000 claims description 9
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- QKLPIYTUUFFRLV-YTEMWHBBSA-N 1,4-bis[(e)-2-(2-methylphenyl)ethenyl]benzene Chemical compound CC1=CC=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=CC=C1C QKLPIYTUUFFRLV-YTEMWHBBSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000013307 optical fiber Substances 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- CNRNYORZJGVOSY-UHFFFAOYSA-N 2,5-diphenyl-1,3-oxazole Chemical compound C=1N=C(C=2C=CC=CC=2)OC=1C1=CC=CC=C1 CNRNYORZJGVOSY-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 claims description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 claims description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 2
- VLDFXDUAENINOO-UHFFFAOYSA-N 4-methyl-2-[4-(4-methyl-5-phenyl-1,3-oxazol-2-yl)phenyl]-5-phenyl-1,3-oxazole Chemical compound CC=1N=C(C=2C=CC(=CC=2)C=2OC(=C(C)N=2)C=2C=CC=CC=2)OC=1C1=CC=CC=C1 VLDFXDUAENINOO-UHFFFAOYSA-N 0.000 claims description 2
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- 230000005251 gamma ray Effects 0.000 claims 1
- 238000001228 spectrum Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- MASVCBBIUQRUKL-UHFFFAOYSA-N POPOP Chemical compound C=1N=C(C=2C=CC(=CC=2)C=2OC(=CN=2)C=2C=CC=CC=2)OC=1C1=CC=CC=C1 MASVCBBIUQRUKL-UHFFFAOYSA-N 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 230000002285 radioactive effect Effects 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
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- 230000004048 modification Effects 0.000 description 4
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- 241000894007 species Species 0.000 description 4
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- -1 peroxide compound Chemical class 0.000 description 3
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- VEXZGXHMUGYJMC-OUBTZVSYSA-N chlorane Chemical compound [36ClH] VEXZGXHMUGYJMC-OUBTZVSYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000005395 radioluminescence Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- 241001268392 Dalla Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000002059 diagnostic imaging Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- DSEZUQJNQKYZOQ-UHFFFAOYSA-M lithium 2-phenoxybenzoate Chemical compound O(C1=CC=CC=C1)C1=C(C(=O)[O-])C=CC=C1.[Li+] DSEZUQJNQKYZOQ-UHFFFAOYSA-M 0.000 description 1
- PSBOOKLOXQFNPZ-UHFFFAOYSA-M lithium;2-hydroxybenzoate Chemical compound [Li+].OC1=CC=CC=C1C([O-])=O PSBOOKLOXQFNPZ-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YERRTOUSFSZICJ-UHFFFAOYSA-N methyl 2-amino-2-(4-bromophenyl)acetate Chemical compound COC(=O)C(N)C1=CC=C(Br)C=C1 YERRTOUSFSZICJ-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000005658 nuclear physics Effects 0.000 description 1
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- 239000002901 radioactive waste Substances 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/203—Measuring radiation intensity with scintillation detectors the detector being made of plastics
- G01T1/2033—Selection of materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K4/00—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens
- G21K2004/08—Conversion screens for the conversion of the spatial distribution of X-rays or particle radiation into visible images, e.g. fluoroscopic screens with a binder in the phosphor layer
Definitions
- the present invention belongs to the field of measurement of radioactivity by the plastic scintillation technique.
- the invention relates to a material for plastic scintillation measurement and method of manufacture, a part comprising the material and its associated measuring device, and the method of plastic scintillation measurement using the material.
- Plastic scintillation measurement consists of determining the presence and / or quantity of one or more radioactive materials, in particular in physics, geology, biology, medicine, dating, environmental monitoring or non-radioactive control. proliferation of nuclear weapons.
- the radioactive material emitting ionizing radiation or an ionizing particle is exposed to a scintillating material called "plastic scintillator" which converts the energy deposit resulting from the interaction radiation / matter in a light radiation (said radioluminescent) measurable by a photon-electron gain converter, such as a photomultiplier.
- the plastic scintillator is known since the mid XXth century. It is described for example in the document “Principles and practice of plastic scintillator design, Radiat. Phys. Chem. , 1993, Vol. 41, No. 1/2, 31-36 "[1]. It is generally in the form of a polymeric matrix in which is inserted a primary fluorophore or a secondary fluorophore.
- the main function of the polymeric matrix is to be a support capable of receiving the energy of the ionizing radiation or of the ionizing particle. After recombination of the excited and / or ionized species which are then formed, this energy is converted into radioluminescent radiation which is transferred to the primary fluorophore and possibly to the secondary fluorophore which can modify the wavelength of the radiation emitted by the primary fluorophore in order to improve detection.
- the primary fluorophore and the secondary fluorophore consist of an aromatic molecule with fluorescent properties (molecule called fluorophore) for detection by scintillation.
- Such a plastic scintillator poses at least one of the following problems:
- the Stokes offset expressed in cm -1 is the difference between the wavenumber of the maximum of the absorption band and that of the maximum of the emission spectrum by fluorescence.
- the stokes offset must be as large as possible, which means that the overlap between the absorption and emission spectra of the scintillator is reduced or even zero, which avoids a loss of photons or their own absorption by the scintillator.
- these modifications may relate to the chemical composition of the polymeric matrix or the plastic scintillator (in particular the concentration of the primary or secondary fluorophore in the polymeric matrix), or the degree of crosslinking of the polymeric matrix.
- One of the aims of the invention is thus to avoid or mitigate one or more of the disadvantages described above, by proposing a material using a carbazole-specific derivative.
- the present invention relates to a material for plastic scintillation measurement comprising (or consisting of):
- N- (2-ethylhexyl) carbazole a primary fluorophore incorporated in the polymer matrix and composed of N- (2-ethylhexyl) carbazole, the monomeric form of N- (2-ethylhexyl) carbazole being spontaneously in physicochemical equilibrium with the exciplex form;
- the material for plastic scintillation measurement according to the invention is also referred to in the present description as the "plastic scintillator". It is characterized in particular by the incorporation of a specific molecule which is N- (2-ethylhexyl) carbazole, also known under the abbreviation "EHCz” and whose general formula (I) is:
- the invention does not consist in the use of a new polymeric matrix, the addition of additive to the plastic scintillator or the development as a primary fluorophore new families of molecules ("quantum dots", organometallic complexes, nanoparticles, ...) to overcome the aforementioned drawbacks, but identifies N- (2-ethylhexyl) carbazole as a new fluorescent probe. All the characteristics necessary for the material for the plastic scintillation measurement according to the invention can thus be essentially limited to a polymer matrix and to the primary fluorophore composed of the N- (2-ethylhexyl) carbazole molecule.
- This molecule performs the function of primary fluorophore or secondary fluorophore: since the impact of the secondary fluorophore is thus reduced, it results in a simplification of the composition of the plastic scintillator by avoiding the difficulty of determining very precisely the appropriate proportion between the primary and secondary fluorophore to obtain radioluminescence radiation and / or Stokes shift which are optimized.
- N- (2-ethylhexyl) carbazole has a high flash point of 170 ° C, good chemical stability, high solubility and miscibility with the compounds used in the manufacture of plastic scintillators, a limited photobleaching, a moderate manufacturing cost, and no significant gas permeability. These properties make it a particularly suitable compound for the manufacture of plastic scintillators.
- the plastic scintillator of the invention can be considered as a pseudo liquid, because the polymer chains constituting all or part of the polymeric matrix are labile and allow a certain freedom of movement to the various constituents of the plastic scintillator. On a macroscopic scale, the plastic scintillator nevertheless retains sufficient mechanical strength to manufacture a part for scintillation detection.
- N- (2-ethylhexyl) carbazole is in the liquid state. This has the advantage of limiting or even avoiding its demixing over time and thus the aging of the plastic scintillator.
- N- (2-ethylhexyl) carbazole can spontaneously form at least one exciplex, namely the combination of at least two identical monomers which exists only in the excited state, and more particularly excimer which is an exciplex formed of only two identical monomers.
- the exciplex form may therefore comprise several types of exciplexes that coexist, for example an exciplex with two identical monomers and an exciplex with three identical monomers.
- N- (2-ethylhexyl) carbazole favors the exciplex form of this molecule with respect to the monomeric form with which it is spontaneously in physico-chemical equilibrium which is then in a minor concentration.
- the maximum of the fluorescence emission spectrum of N- (2-ethylhexyl) carbazole is advantageously centered or close to 420 nm. This wavelength is particularly suitable for the detection, by the current photomultipliers, of the signal from the radioluminescent radiation, which improves the sensitivity of the measurement by plastic scintillation.
- the primary fluorophore used in the material of the invention is composed of N- (2-ethylhexyl) carbazole, a significant proportion of which is in the form of an exciplex.
- N- (2-ethylhexyl) carbazole can be used in the material of the invention.
- the invention is completed by the following objects and / or characteristics, taken alone or according to any of their technically possible combinations.
- a verb such as “understand”, “incorporate”, “include” and its conjugate forms are open terms and do not exclude the presence of element (s) and / or step (s) additional to the element (s) and / or initial step (s) set forth after these terms.
- these open terms also include a particular embodiment in which only the element (s) and / or initial stage (s), to the exclusion of all others, are targeted; in which case the open term also refers to the closed term “consisting of", “constituting", “composing of” and its conjugated forms.
- the use of the undefined article “a” or “an” for an element or a step does not exclude, unless otherwise stated, the presence of a plurality of elements or steps.
- any mass percentage of a component of the plastic scintillator refers to the total mass of the plastic scintillator, the remainder being constituted by the polymeric matrix.
- the material of the invention consists of:
- N- (2-ethylhexyl) carbazole a primary fluorophore incorporated in the polymer matrix and composed of N- (2-ethylhexyl) carbazole, the monomeric form of N- (2-ethylhexyl) carbazole being spontaneously in physicochemical equilibrium with the exciplex form;
- the material then contains no other component.
- the polymeric matrix of the material of the invention is wholly or partly composed of at least one polymer comprising repeating units resulting from the polymerization of monomers or oligomers (which may themselves derive from the polymerization of monomers).
- the chemical structure of the repeating units is thus close to the chemical structure of the monomers, the latter having only been modified by the polymerization reaction.
- a polymer is a general term which also refers to a copolymer, namely a polymer which may comprise repeating units of different chemical structure.
- the monomer or oligomer comprises for example at least one aromatic group (in particular to exploit its photophysical properties), (meth) acrylic (ie acrylic or methacrylic) or vinyl.
- a polymerizable group may be a group comprising an unsaturated carbon-carbon ethylene double bond, such as, for example, the (meth) acrylic or vinyl group.
- this polymerizable group must be capable of being polymerized according to a radical polymerization.
- At least one monomer may be chosen from styrene, vinyltoluene, vinylxylene, vinylbiphenyl, vinylnaphthalene, vinylcarbazole, methyl (meth) acrylate, (meth) acrylic acid or (meth) acrylate 2-hydroxyethyl.
- the monomer is styrene or vinyltoluene.
- the polymer matrix may consist wholly or in part of at least one crosslinked polymer (for example by means of a crosslinking agent), in particular in order to improve the mechanical and / or scintillation properties.
- the crosslinking agent may be a monomer comprising at least two polymerizable functional groups capable, after polymerization, of forming a bridge between two polymer chains. It may be chosen from divinylbenzene, an alkyl diacrylate or dimethacrylate, and the hydrogen carbonate chain of the latter two containing between 2 and 20 carbon atoms.
- the crosslinking agent is 1,4-butanediyl dimethacrylate or divinylbenzene.
- the copolymer obtained may comprise repeating units resulting from the polymerization of the crosslinking agent.
- the material of the invention may comprise 1% by mass at 40 ⁇ 6 (or even at 50%, or 60%) by weight of the primary fluorophore, for example 2% by mass at 45% by weight of the primary fluorophore. Beyond such a concentration, it may possibly have exudation, namely seepage of the primary fluorophore out of the plastic scintillator.
- the material of the invention comprises 1 wt% to 5 wt% of the primary fluorophore (preferably 3 wt% to 5 wt%), or alternatively and preferably 10 wt% to 50 wt% of the primary fluorophore (preferentially 30 wt%). % by mass at 40% by mass).
- the mass percentages of the primary fluorophore, the secondary fluorophore or an additional compound can be determined a posteriori in the plastic scintillator by an analysis technique such as for example the Nuclear Magnetic Resonance (NMR) of the solid or mass spectrometry.
- NMR Nuclear Magnetic Resonance
- Another technique consists in dissolving the plastic scintillator in dichloromethane, precipitating in the methanol the polymer constituting the polymeric matrix, filtering the mixture obtained to recover N- (2-ethylhexyl) carbazole when it is desired, for example, to measure the concentration of the primary fluorophore, then quantify N- (2-ethylhexyl) carbazole by elemental analysis with nitrogen detection.
- the material of the invention may contain one or more materials having no significant impact on the plastic scintillation measurement with the material of the invention or improving some of its properties. These materials are generally dispersed more or less homogeneously in the material.
- the material of the invention may comprise at least one additional compound, such as for example at least one neutron absorbent.
- a neutron absorber has the effect of detecting thermal neutrons by radiative capture.
- the plastic scintillator can thus comprise a mass percentage of 0.1% to 6% of neutron absorbent.
- the neutron absorbent generally comprises a mineral species. Its mass percentage in the material can therefore be measured a posteriori by elemental analysis after grinding of the plastic scintillator. The mass percentage of the neutron absorbent is therefore expressed below by means of the mass percentage of the mineral species (and more particularly a metal species, such as for example gadolinium) in the material.
- the neutron absorbent generally comprises a mineral chemical species. It may be chosen from at least one organometallic complex, typically at least one organometallic complex of lithium, gadolinium, boron, cadmium or a mixture of these complexes, namely a mixture of complexes comprising an identical or different mineral species.
- the organometallic lithium complex is, for example, lithium salicylate and / or lithium phenylsalicylate.
- the organometallic complex of gadolinium is for example chosen from tris (tetramethylheptanedionate) of gadolinium, a gadolinium tricarboxylate or gadolinium tris (acetylacetonate) (Gd (acac) 3). Its concentration in the plastic scintillator is for example between 0.2% by mass and 2.5% by mass of gadolinium.
- the organometallic boron complex is for example chosen from ortiio-carborane, para-carborane or meta-carborane. Its concentration in the plastic scintillator is for example between 1% by weight and 6% by weight of boron.
- the polymeric matrix of the material of the invention also comprises a secondary fluorophore, generally in a content of 0.002% by weight to 0.2% by weight of the secondary fluorophore.
- the secondary fluorophore further enhances the detection of radioluminescent radiation. Its presence is however less essential than for a plastic scintillator of the state of the art, since the material of the invention comprises N- (2-ethylhexyl) carbazole which plays both the role of primary fluorophore and secondary fluorophore .
- the secondary fluorophore is, for example, chosen from 1, 4-di [2- (5-phenyloxazolyl)] benzene (POPOP), 1,4-bis (2-methylstyryl) benzene (Bis-MSB), 9, 10-diphenylanthracene (DPA), 1,4-bis (4-methyl-5-phenyl-2-oxazolyl) benzene (dimethylPOPOP) or mixtures thereof: equivalent molecules which may also be suitable as secondary fluorophore are those which have near or identical spectroscopic properties.
- the invention also relates to a part for plastic scintillation detection comprising a material as defined above according to one or more of the variants described in the present description for this invention.
- material especially in one or more of the variants described which concern the composition and / or the proportion of the constituents of the material (polymeric matrix and primary fluorophore, secondary fluorophore) and of any material that the material may possibly contain (neutron absorbent, ... ).
- This piece may be a unit (such as for example a detector) or a subunit (such as for example an optical fiber) of a structure intended for detection by plastic scintillation.
- the part consists of a detection gantry, a CCD detector (charge coupled device) or an optical fiber.
- the invention also relates to a device for measurement by plastic scintillation comprising a part as defined above according to one or more of the variants described in the present description.
- the device is constituted by a portable device for measuring ionizing radiation, which may optionally comprise a CCD detector or an optical fiber.
- the invention also relates to a method of manufacturing the material of the invention as defined in the present description, in particular according to one or more of the variants described for this material as indicated above.
- the manufacturing process comprises the following steps:
- a) having a polymerization medium comprising: monomers, oligomers or mixtures thereof for forming at least one polymer constituting a polymeric matrix;
- step b) of polymerization of a precursor of the polymer ie the aforementioned monomers and / or oligomers
- the primary fluorophore and the secondary fluorophore are trapped and distributed more or less homogeneously in the polymer matrix. Training.
- the polymerization medium may comprise at least one other species incorporated in the material and intended to confer special properties on it; in particular a neutron absorbent, an additional secondary fluorophore, a crosslinking agent, a polymerization initiator or their mixtures.
- the polymerization medium may comprise 0.001% by weight to 1% by mass of polymerization initiator.
- step b) The polymerization reaction according to step b) can be carried out according to the conditions usually employed by those skilled in the art.
- the polymerization initiator may be chosen from a peroxide compound (for example benzoyl peroxide), a nitrile compound (for example
- the polymerization reaction When the polymerization reaction is carried out with methacrylate monomers, it can be induced by heating the polymerization medium to a suitable temperature (generally between 20 ° C and 140 ° C), or by doping the polymerization medium with 2 -2 dimethoxy-2-phenylacetophenone as a polymerization initiator and then irradiating under UV (for example, at a wavelength of 355 nm).
- a suitable temperature generally between 20 ° C and 140 ° C
- the polymerization reaction in the presence of styrenic monomers can be thermally induced, typically by heating at 20 ° C to 140 ° C.
- Steps a) and b) of the manufacturing method of the invention may be carried out in a mold in order to obtain a part as defined above or a blank of this part.
- the manufacturing method of the invention may also comprise a step c) during which the material is machined in order to obtain the part as defined above.
- the manufacturing method may comprise a step c) during which the material or blank of the workpiece is machined to obtain the workpiece as defined above.
- This machining step consists, for example, in grinding the faces and then polishing them.
- the invention also relates to a material obtained or obtainable by the manufacturing method as defined in the present description, in particular according to one or more of the variants previously described for this material.
- the invention also relates to the use of N- (2-ethylhexyl) carbazole for the detection by plastic scintillation, and more specifically to a method of measuring by plastic scintillation using the material of the invention as defined in the present description, in particular according to one or more of the variants described for this material as indicated above.
- the measuring method comprises the following steps: i) at least one material as defined above is brought into contact with an ionizing radiation or an ionizing particle so that the material emits a radioluminescent radiation; and
- the ionizing radiation or the ionizing particle comes from a radioactive material emitting gamma rays, X-rays, beta particles, alpha particles or neutrons. If necessary, the radioactive material may emit several types of ionizing radiation or ionizing particles.
- the radioluminescent radiation that results from this exposure can be measured according to step ii) with a photodetector, such as for example a photodetector chosen from a photomultiplier, a charge-coupled camera (CCD) English), a CMOS sensor (for "Complementary Metal-Oxide Semiconductor” in English), or any other photon detector whose capture is converted into an electrical signal.
- a photodetector such as for example a photodetector chosen from a photomultiplier, a charge-coupled camera (CCD) English), a CMOS sensor (for "Complementary Metal-Oxide Semiconductor” in English), or any other photon detector whose capture is converted into an electrical signal.
- the measuring method may comprise a step iii) in which the presence and / or quantity of the radioactive material is determined from the measurement of the radioluminescent radiation according to step ii) as is usually done in plastic scintillation.
- step iii) of qualitative measurement and / or Quantitative is described by analogy with plastic scintillation from the document "Engineering Techniques, Liquid Scintillation Radioactivity Measurements, Reference p2552, publication of 10/03/2004" [5].
- the quantitative determination can in particular measure the activity of the radioactive source. It can be performed from a calibration curve.
- This curve is for example such that the number of photons from the radioluminescent radiation emitted for a known radioactive material is correlated with the energy of the incident radiation for this radioactive material. From the solid angle, the distance between the radioactive source and the plastic scintillator, and the activity detected by the measurement method using the plastic scintillator of the invention, it is then possible to quantify the activity of the the radioactive source.
- the fluorescence emission spectra are produced with a spectrofluorimeter.
- EHCz N- (2-ethylhexyl) carbazole
- Figure 1 shows the light absorption spectra of plastic scintillators according to the invention.
- the absorbance expressed in an arbitrary unit is a function of the wavelength of the absorbed light expressed in nanometers.
- Figure 2 shows the fluorescence emission spectrum of plastic scintillators according to the invention.
- the intensity expressed in a normalized unit is a function of the wavelength of the light emitted expressed in nanometers.
- Figure 3 shows the light output of plastic scintillators according to the invention comprising an increasing concentration of EHCz.
- the light yield expressed in arbitrary units is a function of the weight percentage of the EHCz molecule in each plastic scintillator.
- Figure 4 shows the energy spectra of three plastic scintillators when EHCz is used alone at the 3% molar concentration, further mixed with the POPOP secondary fluorophore and mixed with the secondary bis-MSB fluorophore.
- the luminous yield obtained on the ordinate is expressed in arbitrary unit.
- the examples are carried out at atmospheric pressure at room temperature.
- the EHCz molecule is commercially available under the CAS registry number [187148-77-2]. It can be obtained by nucleophilic reaction of previously deprotonated carbazole, with 2-ethylhexyl bromide, according to the following reaction scheme:
- the resulting mixture is stirred for 16 hours at room temperature.
- the obtained EHCz molecule is a colorless oil.
- the molar yield is about 73% for 20 g of synthesized EHCz.
- the characteristics of the proton NMR spectrum of the EHCz molecule are as follows: 1 R NMR (CDCl 3 , 500 MHz) ⁇ 0.86 (t, 3H, 3 J 7.3); 0.91 (t, 3H, 3 J, 7.3); 1.21 - 1.43 (m, 8H); 2.07 (sep, 1H, 3 , 6.7); 4.10-4.21 (m, 2H); 7.39 (d, 4H, 3 J, 8.2); 7.45 (dt, 4H, 3 , 6, 9, 1, 1).
- the properties of the EHCz are as follows: colorless transparent liquid;
- Different plastic scintillators are manufactured according to the characteristics specified in Table 1: they differ in the content of EHCz and the composition of the polymeric matrix which may comprise styrene ("St") and / or 1,4-butanediyl dimethacrylate ( "1.4") (with indication of the mass proportion of each monomer when both are present in the matrix), as well as the possible presence of a secondary fluorophore such as 1, 4-bis- [ 2- (5-phenyloxazolyl) benzene (POPOP) or 1,4-bis (2-methylstyryl) benzene (Bis-MSB) shown below.
- the content of EHC 2 and of secondary fluorophore is expressed as a percentage by mass of the plastic scintillator, the remainder being constituted by the mass percentage of the polymeric matrix.
- the mixture is degassed according to the method of vacuum degassing under vacuum (so-called "freeze-pump-thaw” method). Returned to room temperature, the solution is poured into a mold intended to give the shape of the scintillator. This mold is sealed under an inert atmosphere and then heated at 65 ° C for 10 days. Once the polymerization is complete, the mold is broken to recover the raw plastic scintillator, which is polished to give it its final shape.
- a mixture consisting of purified EHCz (3% by weight), POPOP (0.03% by mass), styrene (77.58% by mass) and 1,4-butanediyl dimethacrylate (19.39% by mass) is introduced. in an inert atmosphere composed of argon in a balloon previously dried under vacuum.
- the mixture is degassed according to the method of vacuum degassing under vacuum. Returned to ambient temperature, the solution obtained is poured into a mold intended to give the shape of the plastic scintillator. This mold is sealed under an inert atmosphere and then heated at 65 ° C for 10 days. Once the polymerization is complete, the mold is broken to recover the raw plastic scintillator, which is polished to give it its final shape. 4.
- Figure 1 shows the absorption spectra of the reference plastic scintillators 8 to 10 "6 ⁇ ITlâSSG of EHCz (solid line) and reference 9 to 20% by mass of the EHCz (dashed line). It shows the interest of incorporating the EHCz in high concentration so that the exciplex formed best emits a luminescence in the field of transparency of the material.
- Figure 2 shows the fluorescence emission spectra of plastic scintillators 1 to 5, 8 to 11.
- the intensity of these spectra is normalized by arbitrarily assigning the value 1 to the value of greater intensity of each spectrum.
- Figure 2 illustrates that the fluorescence emission spectrum is shifted to the higher wavelengths as the concentration of EHCz increases in the plastic scintillator: this hypsochromic shift reflects the increase in the concentration of EHCz in the form of an exciplex at the expense of the monomeric form with which it is in physicochemical equilibrium. The proportion of the excimer form becomes particularly important, especially for concentrations greater than 30% in EHCz.
- the plastic scintillators 1 to 5, 8 to 11 are successively optically coupled with a Rhodorsil optical grease to a photomultiplier powered at high voltage.
- a gamma source of cobalt-60 irradiates each plastic scintillator, which then emits scintillation photons.
- An electronic acquisition device converts the scintillation pulse into an electronic signal which is then amplified by a photomultiplier and then recorded and digitized by an acquisition electronic card.
- the signal obtained is subjected to the following processing sequence: inversion of the signal to make it positive, smoothing, integration of the signal over time, distribution of the value by histogram, then subtraction of the signal obtained under the same conditions without plastic scintillator in order to remove the residual background noise.
- This histogram makes it possible to obtain an energy spectrum, which then gives the light yield obtained for each plastic scintillator as illustrated in FIG. 3.
- Plastic scintillators 6 and 7 respectively comprising POPOP and Bis-MSB as secondary fluorophore are compared to plastic scintillator 3 comprising the same proportion of EHCz (3% by weight).
- the energy spectrum histograms obtained according to the protocol described in Example 6 are illustrated in FIG. 4. This figure shows that EHCz can behave as a primary fluorophore suitable for scintillation.
- the weak pulses result in a crushing to the left of the spectrum which corresponds to the low output energies, indicating that the plastic scintillator is not bright enough. .
- This is explained by the fact that the emission wavelength for 3% by weight of EHCz is not the most suitable for the photomultiplier used and that the plastic scintillator absorbs part of the light that it emits.
- the presence of a secondary fluorophore in the material for plastic scintillation measurement according to the invention is generally of particular interest for the purpose of improving the quality of the measurement.
- the mass percentage of EHCz in the plastic scintillator can then preferably be between 0.002% and 0.2%, or even between 0.01% and 0.1%.
- a plastic scintillator comprising EHCz and a secondary fluorophore is connected to a photomultiplier tube by means of optical grease.
- the plastic scintillator Following exposure to the radioactive material, the plastic scintillator emits scintillation photons which are converted into an electrical signal by the photomultiplier tube fed with high voltage.
- the electrical signal is then acquired and analyzed with an oscilloscope, a spectrometry software or an acquisition electronic card.
- the plastic scintillator is coupled with Rhodorsil RTV141A optical grease to a photomultiplier (model Hamamatsu H1949-51) powered by a high voltage
- This board can be replaced by another equivalent electronic board (for example model CAEN DT5730B) or an oscilloscope (for example model Lecroy Waverunner 640Zi).
- a system energy calibration (scintillator + photomultiplier) is carried out using 2 radioactive sources: one emitting gamma rays in the zone [0-200 keV] and the other one in the zone [500 - 1, 3 MeV].
- This energy calibration is performed by locating the channel corresponding to 80% of the amplitude of the Compton front. For example, if the ordinate of the Compton front corresponds to 100 rounds, the easting of the 80-beat Compton front descent associates the energy of the Compton front (in keV) with the channel.
- a beta-source of chlorine-36 (average energy 251 keV, activity on 2 n equal to a maximum of 3 kBq) is contiguous to the upper face of the plastic scintillator.
- the analysis of the energy spectrum gives a read activity of 2.1 kBq (and therefore an intrinsic efficiency of 70%) and a photoelectric peak centered around 250 keV. 6.3. Quantitative measurement with plastic scintillator 7.
- the plastic scintillator is coupled with Rhodorsil RTV141A optical grease to a photomultiplier (model Hamamatsu H11284 MOD) powered by a high voltage (model CAEN N1470).
- the invention is applicable to the fields where scintillators are used, in particular:
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1652902A FR3049613A1 (fr) | 2016-04-01 | 2016-04-01 | Scintillateur plastique, detecteur, procede de fabrication et procede de mesure par scintillation associes. |
PCT/FR2017/050706 WO2017168086A1 (fr) | 2016-04-01 | 2017-03-28 | Scintillateur plastique, détecteur, procédé de fabrication et procédé de mesure par scintillation associés |
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EP3436546A1 true EP3436546A1 (de) | 2019-02-06 |
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EP17718390.2A Withdrawn EP3436546A1 (de) | 2016-04-01 | 2017-03-28 | Kunststoffszintillator, detektor, zugehöriges herstellungsverfahren und szintillationsmessverfahren |
Country Status (4)
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US (1) | US20190331809A1 (de) |
EP (1) | EP3436546A1 (de) |
FR (1) | FR3049613A1 (de) |
WO (1) | WO2017168086A1 (de) |
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KR102246928B1 (ko) * | 2019-09-25 | 2021-04-30 | 청주대학교 산학협력단 | 플라스틱 섬광체 제조를 위한 3d 프린팅용 레진 |
CN113185628A (zh) * | 2021-03-22 | 2021-07-30 | 中国辐射防护研究院 | 一种聚苯乙烯闪烁微球及其制备方法 |
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FR2969169B1 (fr) * | 2010-12-21 | 2014-05-09 | Commissariat Energie Atomique | Scintillateur organique solide dope par un ou plusieurs elements chimiques |
FR2983310A1 (fr) | 2011-11-25 | 2013-05-31 | Commissariat Energie Atomique | Detecteur a scintillation et procede de fabrication associe |
WO2015038861A1 (en) * | 2013-09-16 | 2015-03-19 | Saint-Gobain Ceramics & Plastics, Inc. | Scintillator and radiation detector including the scintillator |
-
2016
- 2016-04-01 FR FR1652902A patent/FR3049613A1/fr not_active Withdrawn
-
2017
- 2017-03-28 US US16/089,666 patent/US20190331809A1/en not_active Abandoned
- 2017-03-28 EP EP17718390.2A patent/EP3436546A1/de not_active Withdrawn
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