WO2020218356A1 - 耐放射線性無機材料及びその繊維 - Google Patents

耐放射線性無機材料及びその繊維 Download PDF

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Publication number
WO2020218356A1
WO2020218356A1 PCT/JP2020/017362 JP2020017362W WO2020218356A1 WO 2020218356 A1 WO2020218356 A1 WO 2020218356A1 JP 2020017362 W JP2020017362 W JP 2020017362W WO 2020218356 A1 WO2020218356 A1 WO 2020218356A1
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WIPO (PCT)
Prior art keywords
mass
fiber
sio
radiation
inorganic
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.)
Ceased
Application number
PCT/JP2020/017362
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English (en)
French (fr)
Japanese (ja)
Inventor
裕 深澤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Fiber Corp KK
Original Assignee
Nippon Fiber Corp KK
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 PCT/JP2019/039911 external-priority patent/WO2020217568A1/ja
Priority to KR1020217038549A priority Critical patent/KR102678500B1/ko
Priority to US17/605,966 priority patent/US20220177350A1/en
Priority to JP2021516169A priority patent/JP7129679B2/ja
Priority to CA3137805A priority patent/CA3137805A1/en
Priority to EP20793978.6A priority patent/EP3960715A4/en
Application filed by Nippon Fiber Corp KK filed Critical Nippon Fiber Corp KK
Priority to AU2020262012A priority patent/AU2020262012B2/en
Priority to CN202080030765.3A priority patent/CN113727950A/zh
Publication of WO2020218356A1 publication Critical patent/WO2020218356A1/ja
Priority to ZA2021/08158A priority patent/ZA202108158B/en
Anticipated expiration legal-status Critical
Priority to JP2022129239A priority patent/JP7368017B2/ja
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0042—Compositions for glass with special properties for glass comprising or including particular isotopes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/42—Glass
    • 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
    • G21F1/06—Ceramics; Glasses; Refractories
    • 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
    • G21F3/00—Shielding characterised by its physical form, e.g. granules, or shape of the material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2213/00—Glass fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00258—Electromagnetic wave absorbing or shielding materials

Definitions

  • fly ash has been disposed of as waste, but in recent years, as a result of its increasing use as a concrete admixture, the amount of fly ash discarded has been decreasing. However, most of its use depends on the cement sector, and there is concern that if demand for cement stagnates, fly ash, which is disposed of, will start to increase again. For this reason, the development of new uses for fly ash has become an urgent issue.
  • the composition of fly ash varies depending on the raw material coal and the place of origin (power plant, country).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 6-316815
  • Patent Document 1 has 20 to 40% Al 2 O 3 , 35 to 50% SiO 2 , and 15 to 35% Ca O.
  • fly ash fibers characterized by containing 3-12% Fe 2 O 3 and 2-5% Mg O.
  • the Fe 2 O 3 content also contained in fly ash fiber is 3 to 12%. It is desirable that this content is as low as possible. Also, the Fe 2 O 3 content is high. Increasing the amount increases the degree of coloration of the fly ash fiber, which is not preferable. Therefore, a Fe 2 O 3 content of 12% or more is problematic and should be avoided. ”(Ibid., Paragraph).
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2018-531204 (hereinafter, Patent Document 2) is a mineral fiber containing Al 2 O 3 , SiO 2 , CaO, MgO, and Fe 2 O 3 as components. It discloses a mineral fiber characterized by a Fe 2 O 3 content of 5 to 15%. The document states that "increased iron content tends to color the mineral fibers, which is not particularly desirable for applications where the mineral fibers remain visible" (ibid., Paragraph [0005]).
  • JP-A-6-316815 Special table 2018-531204 JP-A-60-231440 JP-A-10-167754
  • the CaO content is preferably 5% by mass or more and 30% by mass or less. If the CaO content is less than 5% by mass, the melting start temperature of the material becomes high, which is not preferable from the viewpoint of energy saving.
  • the CaO content is preferably 10% by mass or more. On the other hand, if the content is more than 30% by mass, the viscosity of the melt is too low and it becomes difficult to form threads.
  • CaO may be abbreviated as C component, and the CaO content may be indicated as [C].
  • the inorganic material of the present invention there are no restrictions on the raw material as long as the ratios of SiO 2 , Al 2 O 3 , Fe 2 O 3 and Ca O fall within the above range. Therefore, compounds of SiO 2 , Al 2 O 3 , Fe 2 O 3 , and Ca O can be prepared as starting materials, but a silica source rich in SiO 2 and an alumina source rich in Al 2 O 3 can be used. , Fe 2 O 3 rich iron oxide source and Ca O rich calcium oxide source are blended and used as a starting material from the viewpoint of raw material cost.
  • the silica source include, but are not limited to, amorphous silica, silica sand, fumed silica, and volcanic ash.
  • fly ash, clinker ash, or coal gasification slag can be used as the silica alumina source
  • copper slag can be used as the iron oxide source
  • steel slag can be used as the calcium oxide source.
  • most of the silica alumina source, the iron oxide source, and the calcium oxide source can be covered by industrial waste.
  • volcanic rocks such as basalt and andesite can also be used as silica-alumina sources.
  • Example 1 30 parts by mass of FA (1) and 70 parts by mass of BA (1) were blended.
  • This sample has the same composition as the sample 3 used in the above-mentioned prior test.
  • the component ratio of this sample is [S] + [A]: 60% by mass, [A] / ([S] + [A]): 0.20, [F]: 16% by mass, [C]: 17 It is by mass% (Table 6).
  • ultrafine fibers (mineral fibers) having a diameter of 50 ⁇ m or less were obtained within 5 hours after the temperature in the furnace reached 1350 ° C. The obtained fiber had a strength that could not be easily cut even when pulled by hand.
  • the fiber sample was irradiated under the following conditions.
  • ⁇ Vickers hardness test> A Vickers hardness test was performed on the fiber sample before irradiation and the fiber sample after irradiation.
  • the test equipment used is the Reichert-Jung Microduromat 4000E and the Leica Telatom 3 light microscope. Considering that the width of the fiber sample is about 20 ⁇ m, the force applied to the sample surface was set to 10 gF (0.098N). As a result of measuring 17 points for each of the samples before and after the irradiation, it was 723 ⁇ 24 kgF / mm 2 before the irradiation and 647 ⁇ 19 kgF / mm 2 after the irradiation.
  • Example 2 The sample was prepared according to the raw material mixing ratio shown as Example 2 in Table 6.
  • the component ratio of this sample is [S] + [A]: 60% by mass, [A] / ([S] + [A]): 0.25, [F]: 19% by mass, [C]: 13 It is by mass% (Table 6).
  • the sample melted and dropped within 5 hours after the temperature in the furnace reached 1350 ° C., and ultrafine fibers (mineral fibers) having a diameter of 50 ⁇ m or less were obtained.
  • the obtained fiber sample was substantially composed of only an amorphous phase, and could not be easily cut even when pulled by hand. The amorphous property is maintained even by irradiation, and the Vickers hardness retention rate is at the same level as in Example 1. As described above, this material is extremely excellent in radiation resistance.
  • the inorganic material of the present invention has excellent radiation resistance, it can be used in the fields of nuclear power, aerospace, and medical care. By using it for the radiation-exposed part of equipment / equipment / member in these fields, the radiation deterioration of the radiation-irradiated part can be suppressed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Glass Compositions (AREA)
PCT/JP2020/017362 2019-04-25 2020-04-22 耐放射線性無機材料及びその繊維 Ceased WO2020218356A1 (ja)

Priority Applications (9)

Application Number Priority Date Filing Date Title
CN202080030765.3A CN113727950A (zh) 2019-04-25 2020-04-22 抗辐射性无机材料及其纤维
US17/605,966 US20220177350A1 (en) 2019-04-25 2020-04-22 Radiation-resistant inorganic material and fiber thereof
JP2021516169A JP7129679B2 (ja) 2019-04-25 2020-04-22 耐放射線性無機材料及びその繊維
CA3137805A CA3137805A1 (en) 2019-04-25 2020-04-22 Radiation-resistant inorganic material and fiber thereof
EP20793978.6A EP3960715A4 (en) 2019-04-25 2020-04-22 RADIATION-RESISTANT INORGANIC MATERIAL AND FIBER THEREOF
KR1020217038549A KR102678500B1 (ko) 2019-04-25 2020-04-22 내방사선성 무기 재료 및 그 섬유
AU2020262012A AU2020262012B2 (en) 2019-04-25 2020-04-22 Radiation-resistant inorganic material and fiber thereof
ZA2021/08158A ZA202108158B (en) 2019-04-25 2021-10-22 Radiation-resistant inorganic material and fiber thereof
JP2022129239A JP7368017B2 (ja) 2019-04-25 2022-08-15 耐放射線性無機繊維及びその製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019083950 2019-04-25
JP2019-083950 2019-04-25
PCT/JP2019/039911 WO2020217568A1 (ja) 2019-04-25 2019-10-09 耐放射線劣化性無機組成物及びその繊維
JPPCT/JP2019/039911 2019-10-09

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WO2020218356A1 true WO2020218356A1 (ja) 2020-10-29

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US (1) US20220177350A1 (https=)
EP (1) EP3960715A4 (https=)
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WO (1) WO2020218356A1 (https=)
ZA (1) ZA202108158B (https=)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021193343A1 (ja) * 2020-03-24 2021-09-30 新日本繊維株式会社 ファイバー、ファイバー製造方法
WO2022034806A1 (ja) * 2020-08-14 2022-02-17 新日本繊維株式会社 フレーク状組成物、フレーク状組成物の製造方法
JPWO2022075169A1 (https=) * 2020-10-06 2022-04-14
JPWO2022215695A1 (https=) * 2021-04-06 2022-10-13
CN116648439A (zh) * 2020-12-28 2023-08-25 新日本繊维株式会社 无机组合物及其纤维以及薄片
WO2024034546A1 (ja) * 2022-08-08 2024-02-15 日本板硝子株式会社 ガラス組成物、ガラス繊維、ガラスフィラー、ガラス繊維の製造方法、及びガラスフィラーの製造方法
EP4265574A4 (en) * 2020-12-15 2025-01-29 Nippon Sheet Glass Company, Limited Reinforcing glass fiber, chopped strand, fiber sheet, and rod
RU2843765C1 (ru) * 2021-04-06 2025-07-18 Ниппон Файбер Корпорейшн Устойчивая к щелочам некристаллическая неорганическая композиция и волокно из неё

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JPS60231440A (ja) 1984-04-10 1985-11-18 ウオルト・デイズニー・プロダクシヨンズ アルカリ耐性ガラス、その製造方法、その物質組成並びにアルカリ耐性ガラスを用いた強化セメント
JPH06316815A (ja) 1992-12-15 1994-11-15 Sansou:Kk フライアッシュファイバー
JPH10167754A (ja) 1996-12-06 1998-06-23 Toshiba Glass Co Ltd 廃棄物固化用ガラス化材及び廃棄物固化ガラス
JP2018531204A (ja) 2015-10-08 2018-10-25 サン−ゴバン イゾベール ミネラルファイバー

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JPS60231440A (ja) 1984-04-10 1985-11-18 ウオルト・デイズニー・プロダクシヨンズ アルカリ耐性ガラス、その製造方法、その物質組成並びにアルカリ耐性ガラスを用いた強化セメント
JPH06316815A (ja) 1992-12-15 1994-11-15 Sansou:Kk フライアッシュファイバー
JPH10167754A (ja) 1996-12-06 1998-06-23 Toshiba Glass Co Ltd 廃棄物固化用ガラス化材及び廃棄物固化ガラス
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021193343A1 (ja) * 2020-03-24 2021-09-30 新日本繊維株式会社 ファイバー、ファイバー製造方法
US12281037B2 (en) 2020-03-24 2025-04-22 Nippon Fiber Corporation Fiber and manufacturing method of the same
WO2022034806A1 (ja) * 2020-08-14 2022-02-17 新日本繊維株式会社 フレーク状組成物、フレーク状組成物の製造方法
JP7641026B2 (ja) 2020-10-06 2025-03-06 新日本繊維株式会社 耐放射線劣化性無機酸化物フレーク
WO2022075169A1 (ja) * 2020-10-06 2022-04-14 新日本繊維株式会社 耐放射線劣化性無機酸化物フレーク
JPWO2022075169A1 (https=) * 2020-10-06 2022-04-14
JP2025081427A (ja) * 2020-10-06 2025-05-27 新日本繊維株式会社 耐放射線劣化性無機酸化物フレーク
EP4265574A4 (en) * 2020-12-15 2025-01-29 Nippon Sheet Glass Company, Limited Reinforcing glass fiber, chopped strand, fiber sheet, and rod
CN116648439A (zh) * 2020-12-28 2023-08-25 新日本繊维株式会社 无机组合物及其纤维以及薄片
CN116648439B (zh) * 2020-12-28 2026-03-31 新日本繊维株式会社 无机组合物及其纤维以及薄片
JPWO2022215695A1 (https=) * 2021-04-06 2022-10-13
WO2022215695A1 (ja) * 2021-04-06 2022-10-13 新日本繊維株式会社 耐アルカリ性非晶質無機組成物及びその繊維
RU2843765C1 (ru) * 2021-04-06 2025-07-18 Ниппон Файбер Корпорейшн Устойчивая к щелочам некристаллическая неорганическая композиция и волокно из неё
WO2024034546A1 (ja) * 2022-08-08 2024-02-15 日本板硝子株式会社 ガラス組成物、ガラス繊維、ガラスフィラー、ガラス繊維の製造方法、及びガラスフィラーの製造方法

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JP2022163187A (ja) 2022-10-25
US20220177350A1 (en) 2022-06-09
JP7368017B2 (ja) 2023-10-24
JPWO2020218356A1 (https=) 2020-10-29
EP3960715A1 (en) 2022-03-02
ZA202108158B (en) 2023-10-25
KR102678500B1 (ko) 2024-06-26
KR20220002500A (ko) 2022-01-06
JP7129679B2 (ja) 2022-09-02
EP3960715A4 (en) 2023-07-26

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