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WO2024198169A1 - Scintillateur à neutrons composite, son procédé de préparation et son utilisation - Google Patents

Scintillateur à neutrons composite, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2024198169A1
WO2024198169A1 PCT/CN2023/108261 CN2023108261W WO2024198169A1 WO 2024198169 A1 WO2024198169 A1 WO 2024198169A1 CN 2023108261 W CN2023108261 W CN 2023108261W WO 2024198169 A1 WO2024198169 A1 WO 2024198169A1
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Prior art keywords
neutron
composite
neutron scintillator
powder
solvent
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PCT/CN2023/108261
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English (en)
Chinese (zh)
Inventor
王采林
姚露
桂婉婷
周洵声
陈龙飞
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Songshan Lake Materials Laboratory
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Songshan Lake Materials Laboratory
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    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • 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
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/615—Halogenides
    • C09K11/616—Halogenides with alkali or alkaline earth metals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T3/00—Measuring neutron radiation
    • G01T3/06—Measuring neutron radiation with scintillation detectors

Definitions

  • the present application relates to the field of radiation detection, and in particular, to a composite neutron scintillator and a preparation method and application thereof.
  • Neutron detection plays an important role in basic physics, nuclear power, radioactive waste storage, homeland security, nuclear medicine and material analysis. Since neutrons are not charged and cannot be detected directly, indirect detection of neutrons is usually achieved by using nuclides that can react with neutrons. At present, most neutron detection uses 3 He neutron detectors, which are expensive. Neutron scintillator is the best solution to replace the expensive 3 He neutron detector. Its principle is to use the nuclides 6 Li, 10 B, 157 Gd contained in the scintillator material or composite material to absorb neutrons and produce high-energy particles, or use gamma rays to excite the scintillator material to produce photons, and collect signals through photomultiplier tubes and electronic systems to achieve neutron detection.
  • 6 Li glass:Ce represented by GS20
  • Ce-doped potassium cryolite structure A 2 LiMX 6 :Ce (Cs 2 LiYCl 6 :Ce, Cs 2 LiYBr 6 :Ce, etc.) has a relatively high light yield, but its growth and preparation process is complex and the production cost is relatively high.
  • the synthesis process of eutectic composite scintillators mostly requires a high temperature and high pressure environment, and the preparation cost is also very high.
  • the Eu-doped eutectic scintillator has a long life and is difficult to be applied to position neutron detectors.
  • the most mature technology currently used is the ZnS:Ag/ 6LiF neutron scintillator screen, which has a relatively high light yield, but a relatively long attenuation life, and is bonded with an adhesive, so it has poor toughness and strength and is easy to break. Therefore, a neutron scintillator with a simple preparation process and that meets the needs of neutron detection is needed.
  • the purpose of the embodiments of the present application is to provide a composite neutron scintillator and a preparation method and application thereof.
  • the neutron scintillator has the characteristics of high light yield, short decay life, and can effectively perform neutron/gamma discrimination, and the preparation process is simple and the cost is low.
  • the present invention provides a composite neutron scintillator, which includes an organic polymer matrix and a Perovskite material powder and neutron absorption material powder are dispersed in an organic polymer matrix, the perovskite material is selected from at least one of Cs 3 Cu 2 I 5 and CsCu 2 I 3 , and the neutron absorption material is selected from at least one of Gd 2 O 3 , 6 LiF and 10 B 2 O 3 .
  • the luminescent material of the composite neutron scintillator is a perovskite material, which is composited with a neutron absorbing material and embedded in an organic polymer matrix to form a large-area scintillator film with good plasticity.
  • the perovskite material is Cs 3 Cu 2 I 5
  • the neutron absorption material is 6 LiF.
  • the mass ratio of the perovskite material powder to the organic polymer matrix is 0.05-1:1.
  • the mass ratio of the perovskite material powder to the neutron absorption material powder is 0.05-1:1.
  • the material of the organic polymer matrix is selected from at least one of polymethyl methacrylate, polystyrene, polyvinyl chloride and polyphenylene oxide.
  • the composite neutron scintillator has a thickness of 0.2-2 mm, a light transmittance of 30%-90%, and a light yield of more than 20,000 photon/MeV.
  • the light transmittance of the scintillator is guaranteed to ensure its detection efficiency.
  • an embodiment of the present application provides a method for preparing the composite neutron scintillator provided in the first aspect, comprising the following steps:
  • the mixed powder is stirred with the solvent until dissolved, and then poured into a mold for molding.
  • the preparation process is simple, and compared with the traditional neutron scintillator, it does not require high-temperature preparation and has low cost.
  • the solvent is selected from at least one of dichloromethane, N,N-dimethylformamide, dimethyl sulfoxide, and alcohols;
  • the molding method is to allow the solvent to evaporate naturally, or to place the mixture at 10-24°C to allow the solvent to evaporate.
  • the method for preparing the perovskite material includes the following steps:
  • an embodiment of the present application provides an application of the composite neutron scintillator provided in the first aspect, and the composite neutron scintillator can be used as a neutron scintillation material for wave-shifting optical fiber, Anger camera, imaging system, and neutron detector.
  • FIG1 is a schematic diagram of the structure of a composite neutron scintillator provided in an embodiment of the present application.
  • FIG2 is a schematic diagram of a microscopic photograph of the perovskite Cs 3 Cu 2 I 5 crystal prepared in Example 1;
  • FIG3 is an XRD pattern of the perovskite Cs 3 Cu 2 I 5 crystal prepared in Example 1;
  • FIG4 is a graph showing the fluorescence quantum efficiency of the perovskite material Cs 3 Cu 2 I 5 prepared in Example 1;
  • FIG5 is a luminescence spectrum of the perovskite material Cs 3 Cu 2 I 5 prepared in Example 1 under X-ray irradiation;
  • FIG6 is a comparison diagram of the light yield of the neutron scintillator of Example 1 and the commercial GS20 scintillator;
  • FIG7 is a neutron scintillator decay life curve of Example 1.
  • FIG. 8 is a neutron scintillator neutron gamma in Example 1 Identification chart
  • FIG9 is a physical photograph of different neutron scintillator samples
  • FIG10 is the absorption spectra of different neutron scintillator samples.
  • an embodiment of the present application provides a composite neutron scintillator, which includes an organic polymer matrix, and a perovskite material powder and a neutron absorption material powder dispersed in the organic polymer matrix.
  • a composite neutron scintillator which includes an organic polymer matrix, and a perovskite material powder and a neutron absorption material powder dispersed in the organic polymer matrix.
  • the perovskite material is selected from at least one selected from Cs 3 Cu 2 I 5 and CsCu 2 I 3
  • the neutron absorption material is selected from at least one selected from Gd 2 O 3 , 6 LiF and 10 B 2 O 3.
  • the perovskite material is Cs 3 Cu 2 I 5
  • the neutron absorption material is 6 LiF.
  • the mass ratio of the perovskite material powder to the organic polymer matrix is generally 0.05-1:1, and can be optionally 0.5:1.
  • the mass ratio of the perovskite material powder to the neutron absorption material powder is 0.05-1:1, and can be optionally 1:1.
  • the mass ratio of the organic polymer matrix to the perovskite material powder and the neutron absorption material powder is 1:0.05-1:0.05-1.
  • the particle size of the perovskite material powder and the neutron absorption material powder the better the effect.
  • the particle size of the perovskite material powder is generally 20-500 ⁇ m, which is easy to prepare; the particle size of the neutron absorption material powder is 1-5 ⁇ m, which can be directly purchased and obtained by grinding.
  • the composite neutron scintillator has a thickness of 0.2-2 mm, a light transmittance of 30%-90%, and a light yield of more than 20,000 photon/MeV, illustratively, about 23,000 photon/MeV.
  • an embodiment of the present application provides a method for preparing the above-mentioned composite neutron scintillator, which comprises the following steps:
  • the solvent is selected from at least one of dichloromethane, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and alcohols.
  • the mixed powder is dissolved in the solvent, subjected to ultrasonic dispersion treatment until uniformly dispersed, and poured into a mold for molding.
  • the molding method is to allow the solvent to evaporate naturally, or to place the solvent at a certain temperature (such as 10-24°C) to evaporate.
  • the embodiment of the present application provides an application of the above-mentioned composite neutron scintillator, and the composite neutron scintillator can be used as a neutron scintillation material for wave-shifting optical fiber, Anger camera, imaging system, and neutron detector.
  • This embodiment provides a neutron scintillator, and the preparation process thereof is as follows:
  • the ratio of CuI and CsI is 2:3.
  • the stabilizer may be one of Tween 80, citric acid, oleic acid, ethylenediaminetetraacetic acid, polyvinylpyrrolidone, etc., and in this embodiment, Tween 80 is used.
  • the solid powder was tested, and a micrograph of the solid powder is shown in FIG2 , and an XRD pattern is shown in FIG3 .
  • the phase structure of the crystal is Cs 3 Cu 2 I 5 (corresponding to card PDF#45-0077), belonging to the Pbnm (62) space group.
  • the fluorescence quantum efficiency of the perovskite material Cs 3 Cu 2 I 5 was tested using an integrating sphere with BaSO 4 built in.
  • the test graph is shown in FIG4 . After calculating the test results, the quantum efficiency was obtained to be 60.3%.
  • the luminescence spectrum of the perovskite material Cs 3 Cu 2 I 5 under X-ray irradiation is shown in FIG5 .
  • the luminescence peak is located at about 440 nm, which is a typical blue luminescence (bright blue light is emitted under X-ray irradiation).
  • This luminescence band corresponds to the high quantum efficiency band of PMT, which is conducive to neutron detection.
  • the type of solvent can be dichloromethane, DMF, DMSO, alcohols, etc.
  • the solvent in this embodiment is dichloromethane.
  • the molding process can be a natural volatilization of the solvent, or volatilization at a certain temperature.
  • the volatilization temperature is determined by the boiling point of the selected solvent. In this embodiment, natural volatilization is used.
  • the shape of the mold can be cylindrical, square, etc.
  • the mold used is cylindrical.
  • the light yield comparison diagram of the neutron scintillator and the commercial GS20 scintillator is shown in FIG6 , where the radiation source is 252 Cf, and the commercial GS20 (whose light yield is about 6000 photons/MeV) is used as the calibration object.
  • the test results show that the neutron scintillator in this embodiment
  • the light output of the neutron scintillator Cs 3 Cu 2 I 5 / 6 LiF/PMMA is about 4 times that of GS20, which is equivalent to a light output of about 23,000 photons/MeV.
  • the decay lifetime curve of the neutron scintillator is shown in FIG7 .
  • the radiation source is 252 Cf.
  • the radiation decay lifetime is fitted and the decay lifetime is obtained to be about 253 ns.
  • the neutron gamma The discrimination diagram is shown in Figure 8.
  • the discrimination method uses image Non-negative matrix method: First, the radiation reaction events are measured under different radiation sources ( 60 Co, 252 Cf, 137 Cs, background (Bg)), and the measured events are formed into image signals, and a two-dimensional image is formed through an algorithm. The different shades of color in Figure 8 represent the signals formed by different events. From Figure 8, it is easy to distinguish the signals formed by neutron radiation and the signals formed by gamma radiation.
  • the neutron scintillator has a high light yield, a short lifespan, and a high neutron gamma discrimination rate (2 ⁇ 10 5 ).
  • This embodiment provides a neutron scintillator, and its preparation process is different from that of embodiment 1 in that:
  • This embodiment provides a neutron scintillator, and its preparation process is different from that of embodiment 1 in that:
  • This embodiment provides a neutron scintillator, and its preparation process is different from that of embodiment 1 in that:
  • This embodiment provides a neutron scintillator, and its preparation process is different from that of embodiment 1 in that:
  • This embodiment provides a neutron scintillator, and its preparation process is different from that of embodiment 1 in that:
  • This embodiment provides a neutron scintillator, and its preparation process is different from that of embodiment 1 in that:
  • This embodiment provides a neutron scintillator, and its preparation process is different from that of embodiment 1 in that:
  • Embodiment 1, Embodiment 4-6, and Embodiment 8 are neutron scintillator samples prepared by using different addition ratios of perovskite materials.
  • Embodiment 1, Embodiment 4-6, and Embodiment 8 are neutron scintillator samples prepared by using different addition ratios of perovskite materials.
  • the composite neutron scintillator of the embodiment of the present application has the characteristics of high light yield, short decay life, and can effectively perform neutron/gamma discrimination, and has a simple preparation process and low cost.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Molecular Biology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Measurement Of Radiation (AREA)
  • Luminescent Compositions (AREA)

Abstract

Des modes de réalisation de la présente demande concernent un scintillateur à neutrons composite, son procédé de préparation et son utilisation, se rapportant au domaine de la détection de rayonnement. Le scintillateur à neutrons composite comprend : une matrice polymère organique ; et une poudre de matériau de pérovskite et une poudre de matériau d'absorption de neutrons qui sont dispersées dans la matrice polymère organique. Le matériau de pérovskite est choisi parmi Cs3Cu2I5 et/ou CsCu2I3, et le matériau d'absorption de neutrons est choisi parmi Gd2O3 et/ou 6LiF et/ou 10B2O3. Le procédé de préparation comprend principalement : le broyage uniforme du polymère organique, du matériau de pérovskite et du matériau d'absorption de neutrons pour obtenir une poudre mélangée ; l'agitation et le mélange de la poudre mélangée avec un solvant jusqu'à ce que la poudre mélangée soit dissoute ; et le versement du mélange dans un moule pour moulage. Le scintillateur à neutrons composite est caractérisé par un rendement lumineux élevé, une durée de désintégration réduite et une capacité de réalisation efficace d'une discrimination neutron/gamma, et présente un procédé de préparation simple et un faible coût.
PCT/CN2023/108261 2023-03-29 2023-07-19 Scintillateur à neutrons composite, son procédé de préparation et son utilisation Ceased WO2024198169A1 (fr)

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CN202310324742.9 2023-03-29
CN202310324742.9A CN118725845A (zh) 2023-03-29 2023-03-29 一种复合中子闪烁体及其制备方法与应用

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101443679A (zh) * 2006-05-26 2009-05-27 塞莫尼根分析技术有限责任公司 中子和γ射线监测器
US20110303852A1 (en) * 2010-06-14 2011-12-15 Saint-Gobain Ceramics & Plastics, Inc. Scintillator including a scintillator particulate and a polymer matrix
CN114411252A (zh) * 2022-01-24 2022-04-29 中国科学院上海硅酸盐研究所 一种新型中子探测用类钙钛矿结构闪烁体及其制备方法和应用
CN114774109A (zh) * 2022-05-18 2022-07-22 成都理工大学 一种无铅钙钛矿聚合物闪烁体制备方法及应用
CN115074116A (zh) * 2021-03-16 2022-09-20 中国科学院理化技术研究所 一种富氢二维钙钛矿快中子闪烁体材料及其制备方法和应用
CN115639587A (zh) * 2021-07-19 2023-01-24 松山湖材料实验室 提高粉末状闪烁体对高能射线探测性能的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101443679A (zh) * 2006-05-26 2009-05-27 塞莫尼根分析技术有限责任公司 中子和γ射线监测器
US20110303852A1 (en) * 2010-06-14 2011-12-15 Saint-Gobain Ceramics & Plastics, Inc. Scintillator including a scintillator particulate and a polymer matrix
CN115074116A (zh) * 2021-03-16 2022-09-20 中国科学院理化技术研究所 一种富氢二维钙钛矿快中子闪烁体材料及其制备方法和应用
CN115639587A (zh) * 2021-07-19 2023-01-24 松山湖材料实验室 提高粉末状闪烁体对高能射线探测性能的方法
CN114411252A (zh) * 2022-01-24 2022-04-29 中国科学院上海硅酸盐研究所 一种新型中子探测用类钙钛矿结构闪烁体及其制备方法和应用
CN114774109A (zh) * 2022-05-18 2022-07-22 成都理工大学 一种无铅钙钛矿聚合物闪烁体制备方法及应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG QIAN, WANG CHENG’ER, WANG ZHIHUA, SUN XILEI, NIKL MARTIN, OUYANG XIAOPING, WU YUNTAO: "Achieving Efficient Neutron and Gamma Discrimination in a Highly Stable 6 Li-Loaded Cs 3 Cu 2 I 5 Perovskite Scintillator", JOURNAL OF PHYSICAL CHEMISTRY LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 13, no. 39, 6 October 2022 (2022-10-06), US , pages 9066 - 9071, XP093216819, ISSN: 1948-7185, DOI: 10.1021/acs.jpclett.2c02643 *

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