CN113999043A - 一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法 - Google Patents
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法 Download PDFInfo
- Publication number
- CN113999043A CN113999043A CN202111268562.0A CN202111268562A CN113999043A CN 113999043 A CN113999043 A CN 113999043A CN 202111268562 A CN202111268562 A CN 202111268562A CN 113999043 A CN113999043 A CN 113999043A
- Authority
- CN
- China
- Prior art keywords
- temperature
- boron carbide
- neutron shielding
- shielding material
- interpenetrating
- 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.)
- Pending
Links
- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 103
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 93
- 239000000919 ceramic Substances 0.000 title claims abstract description 80
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000006260 foam Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 12
- 239000002861 polymer material Substances 0.000 claims abstract description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 238000001272 pressureless sintering Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000005995 Aluminium silicate Substances 0.000 claims description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000012700 ceramic precursor Substances 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 11
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 11
- 229940075613 gadolinium oxide Drugs 0.000 claims description 11
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000001029 thermal curing Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- JEUDBARJOQFTCD-UHFFFAOYSA-K C(C=C)(=O)[O-].[Gd+3].C(C=C)(=O)[O-].C(C=C)(=O)[O-] Chemical compound C(C=C)(=O)[O-].[Gd+3].C(C=C)(=O)[O-].C(C=C)(=O)[O-] JEUDBARJOQFTCD-UHFFFAOYSA-K 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract 2
- 239000004408 titanium dioxide Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- -1 polyethylene Polymers 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000011153 ceramic matrix composite Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 229910000712 Boron steel Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- KWGASIUWELSTHP-UHFFFAOYSA-N boron;phenol Chemical compound [B].OC1=CC=CC=C1 KWGASIUWELSTHP-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5057—Carbides
- C04B41/5058—Boron carbide
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/06—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
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/10—Organic substances; Dispersions in organic carriers
-
- C—CHEMISTRY; METALLURGY
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3821—Boron carbides
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/606—Drying
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Products (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明公开了一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法,属于泡沫陶瓷材料和聚合物复合材料制备技术领域;本发明采用有机泡沫浸渍法制备碳化硼泡沫陶瓷的前驱体,采用莫来石结构增强碳化硼泡沫陶瓷,采用氩气保护、无压烧结的方式煅烧碳化硼泡沫陶瓷,采用真空浸渍的方式填充液态树脂于泡沫陶瓷的孔隙,采用热固化的方式原位固化液态树脂于孔隙中,最后形成一种具有互穿相的新型中子屏蔽材料。本发明所制备的中子屏蔽材料质轻、耐高温、耐辐照、耐化学腐蚀、力学强度高且中子屏蔽性能好;在保持陶瓷材料作为高温结构材料的前提下,还兼具聚合物材料的优良特性。
Description
技术领域
本发明属于泡沫陶瓷材料和聚合物复合材料制备技术领域,具体涉及一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法。
背景技术
随着国防科研、放射医学和核电工业的迅速发展,对辐射屏蔽材料的性能要求越来越高。由于中子不带电且具有很强的穿透性,会直接与物质中的原子核相互作用,与同等能量的α、β和γ等射线相比,对人体造成的损伤更大,因此研制出优良的中子屏蔽材料尤为重要。多年来,我国在中子辐射防护材料方面积累了一定技术和经验,屏蔽混凝土、高硼钢和铅硼聚乙烯等屏蔽材料已被广泛用于核反应堆屏蔽系统。但随着快堆、小型核动力堆以及其他可移动辐射源应用的增加,上述屏蔽材料已经很难满足其辐射防护设计的特殊需求:一般屏蔽混凝土单位体积屏蔽率低,体积大难以移动,且其强度相对较低;传统高硼钢强度很高,但添加过多元素(尤其是重金属元素)会导致材料强韧性破坏,且含硼钢中硼含量普遍偏低,其对热中子屏蔽效果较差;铅硼聚乙烯具有优异的热中子和γ射线屏蔽效果,但由于铅和B4C难以均匀分布,环境友好性差,且聚乙烯耐热温度低,抗辐照效应差,力学强度不高,限制了其使用。因此,制备高性能的新型中子辐射防护复合材料已成为中子防护领域亟待解决的重要课题。
目前,陶瓷基复合材料和聚合物复合材料凭借其本身的优良特性,开始作为新兴的中子辐射防护材料为人关注。陶瓷基复合材料具有高硬度、高耐磨性、耐高温和耐腐蚀性,同时具有较高的抗弯强度和抗压强度;而高分子复合材料质轻、耐辐照、耐腐蚀,易塑形,其高的延展性同时也能弥补陶瓷基复合材料抗拉强度不高的缺陷。在中子防护领域,陶瓷基复合材料应用最多的陶瓷材料为碳化硼陶瓷;碳化硼陶瓷一般较为坚硬,但由于碳化硼的熔点高达2350℃,塑性差,晶界移动阻力很大,因此纯碳化硼陶瓷的烧结条件苛刻,制备困难,工艺成本极高。为制备陶瓷与聚合物结合为互穿相的复合材料,碳化硼陶瓷选择制备为多孔泡沫状,导致煅烧时无法使用热压烧结的烧结方式,进一步导致了碳化硼陶瓷烧结的困难。为此,需选用合适的方法和手段,降低生产成本的同时保留碳化硼陶瓷骨架原有的强度,制备性能优异的碳化硼陶瓷骨架,是目前需要解决的问题。
发明内容
本发明提供一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法,采用氩气保护、无压烧结的方式煅烧碳化硼泡沫陶瓷,具有产量大、不限制产品形状、生产成本低等特点。
为解决以上技术问题,本发明采用以下技术方案:
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,所述屏蔽材料为聚合物材料在陶瓷材料骨架中原位固化形成互穿相的结构,所述陶瓷材料与聚合物材料在彼此的体系中表现为三维网状结构,两相间相互纠缠形成三维拓扑结构;所述陶瓷材料为氧化铝、高岭土、碳化硼和金属氧化物烧结而成,所述聚合物材料为液态硼改性酚醛树脂热固化而成。
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,包括以下步骤:
步骤一、配料:将10~30份质量的碳化硼微粉、40~60份质量的氧化铝微粉、10~30份质量的超细高岭土,以及烧结助剂5~10份金属氧化物混合,得到100份质量的混合粉体Ⅰ;再向25~100份质量的去离子水中加入0.3~1.0份质量的聚羧酸盐、0.3~1.5份质量的羧甲基纤维素钠、0.3~1.5份质量的聚乙烯醇和0.1~2.0份质量的无水乙醇,得到混合溶液Ⅱ;
步骤二、混料、浸渍:将步骤一得到的混合粉体Ⅰ、混合溶液Ⅱ进行球磨1~4h,制得最后浆体Ⅲ;将聚氨酯海绵浸入10wt%NaOH溶液20~30min预处理,取出海绵进行冲洗、干燥,随后再浸入浆体Ⅲ中,除去多余的浆料,制得碳化硼泡沫陶瓷的前驱体;
步骤三、煅烧:将浸渍后的碳化硼泡沫陶瓷前驱体进行干燥;将干燥后的碳化硼泡沫陶瓷前驱体进行煅烧,煅烧采用氩气保护、无压烧结的方式,升温速率采用程序控温的方式;最后在最终温度1300~1500℃下保温2~5h,随炉冷却至室温,即得到碳化硼泡沫陶瓷;
步骤四、填充、固化:将碳化硼泡沫陶瓷用硅烷偶联剂kh-550进行预处理并烘干,随后将液态树脂水浴加热40~80℃,加入具有中子屏蔽性能的功能微粉机械搅拌20~60min,将混合均匀的液态树脂和碳化硼泡沫陶瓷抽真空至-10~40kpa保持0.5h释压,随后采用阶段升温的方式进行热固化处理,在最终固化温度保温2~3h后随炉冷却至室温,即得到互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料。
以上所述步骤中,步骤一中所述的烧结助剂为氧化镁、氧化钇或二氧化钛中的一种或多种的混合,其中氧化镁、氧化钇或二氧化钛的平均粒径≤100nm;
所述的碳化硼微粉的粒径≤4μm;
所述的氧化铝微粉的粒径≤2μm;
所述的超细高岭土的粒径≤5μm;
步骤二中所述球磨的球料比为(1~3):1,球磨时间为1~4h;所述的聚氨酯海绵为10ppi,尺寸为50mm*50mm*20mm;通过离心甩浆和鼓风喷吹的方式除去多余的浆料,重复该方法1~4次;
步骤三中碳化硼泡沫陶瓷前驱体干燥的过程为:在室温下自然干燥12~24h,随后放置于干燥箱内50~80℃干燥12~24h;所述的碳化硼泡沫陶瓷前驱体煅烧的过程为:在室温~200℃时,升温速率2℃/min;在200~650℃时,升温速率1℃/min;在650~900℃时,升温速率2℃/min;在900℃保温1h;在900~终点温度时,升温速率3℃/min;最后在终点温度保温3h,随炉冷却至常温;
步骤四中所述的液态树脂为热固性硼改性酚醛树脂,所述热固性硼改性酚醛树脂中硼元素质量百分含量为15%;所述的具有中子屏蔽性能的功能微粉为硼酸锌、碳化硼、氮化硼、氧化钆和丙烯酸钆的一种或多种的混合
所述的热固化过程为:按10℃/h升温,室温~80℃,80℃保温12~18h;80~90℃,90℃保温1h;90~100℃,100℃保温1h;100~110℃,110℃保温1h;最后110~120℃,120℃保温2~3h,后处理150℃保温3h随炉冷却。
有益效果:本发明提供了一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法,采用氩气保护、无压烧结的方式煅烧碳化硼泡沫陶瓷,具有产量大、不限制产品形状、生产成本低等特点,适合于规模化生产。本发明采用高岭土与氧化铝高温下产生的莫来石结构来补强无压烧结碳化硼陶瓷时由于碳化硼烧结的致密性不高造成硬度和强度稳定性差的缺陷;采用耐高温的液态树脂在碳化硼陶瓷骨架中原位固化的方式,使新型中子屏蔽材料形成了互穿相的结构;其中陶瓷材料与聚合物材料在彼此的体系中表现为三维网状结构,两相间相互纠缠从而形成三维拓扑结构;本发明设计的新型中子屏蔽材料除了满足中子屏蔽的需求以外,还能在300℃的高温场景长期使用,并且化学稳定性好,耐腐蚀性和耐辐照性能优异。本发明在保持陶瓷材料作为高温结构材料的前提下,新型中子屏蔽材料兼具聚合物材料化学稳定性高,耐腐蚀、耐辐照和延展性好等优良特性,为新型中子屏蔽材料的设计与应用提供了一种思路。
附图说明
图1为本发明实施例制备的泡沫陶瓷骨架的SEM图(A组-E组)和中子屏蔽材料的SEM图;
图2为实施例4制备的新型中子屏蔽材料的TG-DTG图;
图3为本发明中子屏蔽材料制备过程示意图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明:为避免重复,先将本具体实施方式所要涉及的技术参数统一描述如下,实施例中将不赘述:
所述的烧结助剂为二氧化钛微粉,二氧化钛的平均粒径≤100nm。
所述的碳化硼微粉的粒径≤4μm。
所述的氧化钆微粉纯度99.9%,metals basis,购买于阿拉丁试剂公司。
所述的氧化铝微粉的粒径≤2μm
所述的超细高岭土微粉的粒径≤5μm
所述的聚氨酯海绵为10ppi,尺寸为50mm*50mm*20mm。
所述的液态树脂为热固性硼改性酚醛树脂,硼元素质量百分含量为15%。
所述的碳化硼泡沫陶瓷前驱体煅烧的程序控温的方式为:在室温~200℃时,升温速率2℃/min;在200~650℃时,升温速率1℃/min;在650~900℃时,升温速率2℃/min;在900℃保温1h;在900~终点温度时,升温速率3℃/min;最后在终点温度保温3h,随炉冷却至常温。
所述的硼改性酚醛树脂以阶段升温的方式热固化,按10℃/h升温,所述的热固化过程为:室温~80℃,80℃保温12~18h;80~90℃,90℃保温1h;90~100℃,100℃保温1h;100~110℃,110℃保温1h;最后110~120℃,120℃保温2~3h,后处理150℃保温3h随炉冷却。
实施例1
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,制作步骤如下:
步骤一、配料:(设定为粉体配比A)将30份质量的碳化硼微粉、55份质量的氧化铝微粉、10份质量的超细高岭土,以及烧结助剂5份二氧化钛微粉混合,得到100份质量的混合粉体Ⅰ;再向61.3份质量的去离子水中加入0.5份质量的聚羧酸盐、0.7份质量的羧甲基纤维素钠、0.7份质量的聚乙烯醇和1.0份质量的无水乙醇,得到混合溶液Ⅱ;
步骤二、混料、浸渍:以重量计按一定比例称取磨球,球料比=1:1;将混合粉体Ⅰ、混合溶液Ⅱ和磨球逐个加入球磨罐中,机械球磨3h,制得最后浆体Ⅲ;将预处理的聚氨酯海绵浸入浆体Ⅲ中,通过离心甩浆和鼓风喷吹的方式除去多余的浆料,重复该方法3次,最后制得碳化硼泡沫陶瓷的前驱体;
步骤三、煅烧:将浸渍后的碳化硼泡沫陶瓷前驱体在室温下自然干燥24h,随后放置于干燥箱内60℃干燥12h;将干燥后的碳化硼泡沫陶瓷前驱体放置于气氛炉中煅烧,煅烧采用氩气保护、无压烧结的方式,升温速率采用程序控温的方式;最后在最终温度1350℃下保温3h,随炉冷却至室温,即得到碳化硼泡沫陶瓷;
步骤四、填充、固化:将碳化硼泡沫陶瓷用硅烷偶联剂kh-550进行预处理并烘干,随后将液态树脂水浴加热60℃,加入具有中子屏蔽性能的功能微粉碳化硼机械搅拌30min,混合均匀后将含有20wt%碳化硼的混合液和碳化硼泡沫陶瓷放置于同一玻璃模具中;将模具放置于真空干燥箱内抽真空至-20kpa保持0.5h释压,随后采用阶段升温的方式对液态树脂进行热固化处理,在最终固化温度保温3h后随炉冷却至室温,即得到互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料。
本实施例1所制备的新型中子屏蔽材料,经检测:碳化硼陶瓷骨架的体积密度为0.43g/cm3,新型中子屏蔽材料的体积密度为1.31g/cm3; 碳化硼陶瓷骨架的常温耐压强度为0.96 MPa,新型中子屏蔽材料的常温耐压强度为60.47MPa;采用300mCi Am-Be中子源对新型中子屏蔽材料(厚度为12~13mm)进行辐照,热中子屏蔽率为77%。
实施例2
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,本实例所述的制作步骤与实施例1相同,所不同的是:微粉的组成配比改为25份质量的碳化硼微粉、55份质量的氧化铝微粉、15份质量的超细高岭土,以及烧结助剂5份二氧化钛微粉——设定为粉体配比B。
其余步骤及参数与实施例1一致,不作雷同赘述。
本实施例2所制备的新型中子屏蔽材料,经检测:碳化硼陶瓷骨架的体积密度为0.67g/cm3,新型中子屏蔽材料的体积密度为1.30g/cm3; 碳化硼陶瓷骨架的常温耐压强度为1.31 MPa,新型中子屏蔽材料的常温耐压强度为45.63MPa;采用300mCi Am-Be中子源对新型中子屏蔽材料(厚度为12~13mm)进行辐照,热中子屏蔽率为75%。
实施例3
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,本实例所述的制作步骤与实施例1相同,所不同的是:微粉的组成配比改为20份质量的碳化硼微粉、55份质量的氧化铝微粉、20份质量的超细高岭土,以及烧结助剂5份二氧化钛微粉——设定为粉体配比C。
其余步骤及参数与实施例1一致,不作雷同赘述。
本实施例3所制备的新型中子屏蔽材料,经检测:碳化硼陶瓷骨架的体积密度为0.66g/cm3,新型中子屏蔽材料的体积密度为1.18g/cm3; 碳化硼陶瓷骨架的常温耐压强度为1.04 MPa,新型中子屏蔽材料的常温耐压强度为62.51MPa;采用300mCi Am-Be中子源对新型中子屏蔽材料(厚度为12~13mm)进行辐照,热中子屏蔽率为74%。
实施例4
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,本实例所述的制作步骤与实施例1相同,所不同的是:微粉的组成配比改为15份质量的碳化硼微粉、55份质量的氧化铝微粉、25份质量的超细高岭土,以及烧结助剂5份二氧化钛微粉——设定为粉体配比D。
其余步骤及参数与实施例1一致,不作雷同赘述。
本实施例4所制备的新型中子屏蔽材料,经检测:碳化硼陶瓷骨架的体积密度为0.54g/cm3,新型中子屏蔽材料的体积密度为1.22g/cm3; 碳化硼陶瓷骨架的常温耐压强度为0.94 MPa,新型中子屏蔽材料的常温耐压强度为86.24MPa;采用300mCi Am-Be中子源对新型中子屏蔽材料(厚度为12~13mm)进行辐照,热中子屏蔽率为73%。
实施例5
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,本实例所述的制作步骤与实施例1相同,所不同的是:微粉的组成配比改为10份质量的碳化硼微粉、55份质量的氧化铝微粉、30份质量的超细高岭土,以及烧结助剂5份二氧化钛微粉——设定为粉体配比E。
其余步骤及参数与实施例1一致,不作雷同赘述。
本实施例5所制备的新型中子屏蔽材料,经检测:碳化硼陶瓷骨架的体积密度为0.77g/cm3,新型中子屏蔽材料的体积密度为1.26g/cm3; 碳化硼陶瓷骨架的常温耐压强度为0.77 MPa,新型中子屏蔽材料的常温耐压强度为69.77MPa;采用300mCi Am-Be中子源对新型中子屏蔽材料(厚度为12~13mm)进行辐照,热中子屏蔽率为67%。
如图1所示,前五张(A组-E组)为实施例1~5制备的泡沫陶瓷骨架的SEM图,最后一张为实施例4制备的互穿型中子屏蔽材料的SEM图,相同煅烧温度下,从实施例1~5,随着高岭土含量的增加,鳞片状的一次莫来石的生成逐渐减少,针状的二次莫来石结构逐渐增加,且二次莫来石的形状逐渐由细长针状变为短柱形的簇射状,颗粒堆积开始密集,孔隙渐渐变小,骨架体系宏观呈现收缩致密化趋势,这是因为高岭土与氧化铝微粉形成二次莫来石,产生一定的收缩;同时,从SEM图中看到粉料颗粒的团聚结合,对于陶瓷骨架的收缩也产生了影响。
从实施例4互穿型中子屏蔽材料的SEM图可以看出,硼改性树脂界面呈现鳞片型脆性断裂特性,莫来石/碳化硼泡沫陶瓷界面呈现海浪型脆性断裂特性,两相分辨明显。
如图2实施例4制备的新型中子屏蔽材料的TG-DTG图所示,互穿型中子屏蔽材料微熵失重曲线(DTG)中有两个明显的失重峰,分别是115℃、552℃;根据文献的研究,第一个失重峰为硼酚醛树脂的固化过程,起始点80℃为硼酚醛树脂的近似凝胶温度,峰值点115℃为硼酚醛树脂的固化温度;第二个失重峰为硼酚醛树脂的热裂解过程,起始点为330℃,峰值点为522℃,此过程为硼氧键、亚甲基键的断裂以及苯环脱氢等反应,力学性能急剧恶化。
从中子屏蔽材料热失重曲线(TG)中可以看出,复合材料失重5%时,温度为181℃,此温度为硼酚醛树脂的后处理温度;复合材料失重10%时,温度为418 ℃;结合TG-DTG曲线,可推断出,新型中子屏蔽复合材料的高温服役温度为180~330℃,在此温度区间复合材料可以长期应用。
实施例6
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,本实例所述的制作步骤与实施例1相同,所不同的是:(配比B)微粉的组成配比改为25份质量的碳化硼微粉、55份质量的氧化铝微粉、15份质量的超细高岭土,以及烧结助剂5份二氧化钛微粉;陶瓷骨架的烧结温度改为1400℃;制备的填充液是含有10wt%氧化钆的氧化钆/硼酚醛树脂;
其余步骤及参数与实施例1一致,不作雷同赘述。
本实施例6所制备的新型中子屏蔽材料,经检测:碳化硼陶瓷骨架的体积密度为0.34g/cm3,新型中子屏蔽材料的体积密度为1.34g/cm3; 碳化硼陶瓷骨架的常温耐压强度为0.38 MPa,新型中子屏蔽材料的常温耐压强度为33.84 MPa;采用300mCi Am-Be中子源对新型中子屏蔽材料(厚度为12~13mm)进行辐照,热中子屏蔽率为80%。
实施例7
一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,本实例所述的制作步骤与实施例1相同,所不同的是:(配比B)微粉的组成配比改为25份质量的碳化硼微粉、55份质量的氧化铝微粉、15份质量的超细高岭土,以及烧结助剂5份二氧化钛微粉;陶瓷骨架的烧结温度改为1400℃;制备的填充液是含有20wt%氧化钆的氧化钆/硼酚醛树脂;
其余步骤及参数与实施例1一致,不作雷同赘述。
本实施例7所制备的新型中子屏蔽材料,经检测:碳化硼陶瓷骨架的体积密度为0.34g/cm3,新型中子屏蔽材料的体积密度为1.38g/cm3; 碳化硼陶瓷骨架的常温耐压强度为0.38MPa,新型中子屏蔽材料的常温耐压强度为27.76 MPa;采用300mCi Am-Be中子源对新型中子屏蔽材料(厚度为12~13mm)进行辐照,热中子屏蔽率为88%。
表1 新型中子屏蔽复合材料的配比和性能
编号 | 填充骨架 | 硼酚醛/g | 碳化硼/g | 氧化钆/g | 厚度/mm | 抗压强度/MPa | 热中子屏蔽率 |
实施例1 | 1350-A | 40 | 10 | 0 | 12.70 | 60.47 | 77% |
实施例2 | 1350-B | 40 | 10 | 0 | 12.62 | 45.63 | 75% |
实施例3 | 1350-C | 40 | 10 | 0 | 12.18 | 62.51 | 74% |
实施例4 | 1350-D | 40 | 10 | 0 | 12.35 | 86.24 | 73% |
实施例5 | 1350-E | 40 | 10 | 0 | 12.57 | 69.77 | 67% |
实施例6 | 1400-B | 60 | 0 | 7 | 12.64 | 33.84 | 80% |
实施例7 | 1400-B | 60 | 0 | 15 | 12.57 | 27.76 | 88% |
如表1所示,实施例1~5为20wt%碳化硼/树脂填充,实施例6~7为10wt%和20wt%氧化钆/树脂填充。从实施例1~5中可以看出,不同配比泡沫陶瓷的引入对于互穿相中子屏蔽材料的抗压性能影响很大,而对于热中子的屏蔽性能的增强较小,这是因为在外压力施加情况下,泡沫陶瓷的引入可以引导单一方向的外压力向骨架的三维网络结构分散,减弱单一方向外压力对互穿型中子屏蔽材料的载荷负担,进而增强互穿相的抗压能力;所引入的泡沫陶瓷结构强度越高,互穿型中子屏蔽材料的抗压能力越强;但由于泡沫陶瓷具有较高的显气孔率(70%以上),形成的互穿型中子屏蔽材料热中子的屏蔽性能主要依靠树脂复合材料,骨架热中子屏蔽性能的增强十分有限。
从实施例2、6和7中可以看出,氧化钆可以实现更优的热中子屏蔽效果,但是由于氧化钆和树脂的界面相容性不如碳化硼微粉,形成的互穿型中子屏蔽材料实施例6~7抗压性能不如实施例1~5。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以已设有的前提下出现各种更改和变化。凡在本发明的设计和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料,其特征在于,所述屏蔽材料为聚合物材料在陶瓷材料骨架中原位固化形成互穿相结构,所述陶瓷材料与聚合物材料在彼此的体系中表现为三维网状结构,两相间相互纠缠形成三维拓扑结构。
2.一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,包括以下步骤:
步骤一、配料:将10~30份质量的碳化硼微粉、40~60份质量的氧化铝微粉、10~30份质量的超细高岭土,以及烧结助剂5~10份金属氧化物混合,得到100份质量的混合粉体Ⅰ;再向25~100份质量的去离子水中加入0.3~1.0份质量的聚羧酸盐、0.3~1.5份质量的羧甲基纤维素钠、0.3~1.5份质量的聚乙烯醇和0.1~2.0份质量的无水乙醇,得到混合溶液Ⅱ;
步骤二、混料、浸渍:将步骤一得到的混合粉体Ⅰ、混合溶液Ⅱ进行球磨1~4h,制得最后浆体Ⅲ;将聚氨酯海绵浸入10wt%NaOH溶液20~30min预处理,取出海绵进行冲洗、干燥,随后再浸入浆体Ⅲ中,除去多余的浆料,制得碳化硼泡沫陶瓷的前驱体;
步骤三、煅烧:将浸渍后的碳化硼泡沫陶瓷前驱体进行干燥;将干燥后的碳化硼泡沫陶瓷前驱体进行煅烧,煅烧采用氩气保护、无压烧结的方式,升温速率采用程序控温的方式;最后在最终温度1300~1500℃下保温2~5h,随炉冷却至室温,即得到碳化硼泡沫陶瓷;
步骤四、填充、固化:将碳化硼泡沫陶瓷用硅烷偶联剂kh-550进行预处理并烘干,随后将液态树脂水浴加热40~80℃,加入具有中子屏蔽性能的功能微粉机械搅拌20~60min,将混合均匀的液态树脂和碳化硼泡沫陶瓷抽真空至-10~40kpa保持0.5h释压,随后采用阶段升温的方式进行热固化处理,在最终固化温度保温2~3h后随炉冷却至室温,即得到互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料。
3.根据权利要求2所述的互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,步骤一中所述的烧结助剂的平均粒径≤100nm;所述的碳化硼微粉的粒径≤4μm;所述的氧化铝微粉的粒径≤2μm;所述的超细高岭土的粒径≤5μm。
4.根据权利要求2或3所述的互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,步骤一中所述的烧结助剂为氧化镁、氧化钇、二氧化钛中的一种或多种的混合。
5.根据权利要求2所述的互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,步骤二中所述球磨的球料比为(1~3):1,球磨时间为1~4h。
6.根据权利要求2所述的互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,步骤三中所述碳化硼泡沫陶瓷前驱体干燥的过程为:在室温下自然干燥12~24h,随后放置于干燥箱内50~80℃干燥12~24h。
7.根据权利要求2或6所述的互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,步骤三中所述的碳化硼泡沫陶瓷前驱体煅烧的过程为:在室温~200℃时,升温速率2℃/min;在200~650℃时,升温速率1℃/min;在650~900℃时,升温速率2℃/min;在900℃保温1h;在900~终点温度时,升温速率3℃/min;最后在终点温度保温3h,随炉冷却至常温。
8.根据权利要求2所述的互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,步骤四中所述的液态树脂为热固性硼改性酚醛树脂,所述的具有中子屏蔽性能的功能微粉为硼酸锌、碳化硼、氮化硼、氧化钆和丙烯酸钆的一种或多种的混合。
9.根据权利要求8所述的互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,所述热固性硼改性酚醛树脂中硼元素质量百分含量为15%。
10.根据权利要求2所述的互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料的制备方法,其特征在于,步骤四中所述的热固化过程为:按10℃/h升温,室温~80℃,80℃保温12~18h;80~90℃,90℃保温1h;90~100℃,100℃保温1h;100~110℃,110℃保温1h;最后110~120℃,120℃保温2~3h,后处理150℃保温3h随炉冷却。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111268562.0A CN113999043A (zh) | 2021-10-29 | 2021-10-29 | 一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111268562.0A CN113999043A (zh) | 2021-10-29 | 2021-10-29 | 一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113999043A true CN113999043A (zh) | 2022-02-01 |
Family
ID=79924929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111268562.0A Pending CN113999043A (zh) | 2021-10-29 | 2021-10-29 | 一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113999043A (zh) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114621024A (zh) * | 2022-03-23 | 2022-06-14 | 山东华屹科创纳米材料有限公司 | 一种高纯增韧碳化硼泡沫陶瓷及其制备方法 |
CN114920564A (zh) * | 2022-05-07 | 2022-08-19 | 刘峻廷 | 一种高纯碳化硼管式陶瓷过滤膜制备方法 |
CN115745638A (zh) * | 2022-12-08 | 2023-03-07 | 武汉科技大学 | 一种莫来石-碳化硼轻质耐火材料及其制备方法 |
CN115959909A (zh) * | 2022-12-09 | 2023-04-14 | 武汉科技大学 | 一种B4C-莫来石-NbB2复合陶瓷及其制备方法 |
CN116178895A (zh) * | 2023-02-21 | 2023-05-30 | 哈尔滨理工大学 | 一种高导热环氧树脂复合材料及其制备方法和应用 |
CN116749413A (zh) * | 2023-08-22 | 2023-09-15 | 中核北方核燃料元件有限公司 | 一种耐高温复合屏蔽材料及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3153636A (en) * | 1958-10-31 | 1964-10-20 | Carborundum Co | Porous bodies of controlled densities and methods of making them |
CN102757223A (zh) * | 2012-07-04 | 2012-10-31 | 山东大学 | 一种稀土硼化物/碳化硼复合中子吸收材料及其制备方法 |
CN104311136A (zh) * | 2014-10-22 | 2015-01-28 | 山东理工大学 | 一种氮化硅、碳化硅结合碳化硼泡沫陶瓷的制备方法 |
CN106699185A (zh) * | 2016-11-30 | 2017-05-24 | 潘云清 | 一种铝合金复合材料 |
CN108863442A (zh) * | 2018-06-13 | 2018-11-23 | 南京航空航天大学 | 一种中子屏蔽复合材料及其制备方法 |
CN109279909A (zh) * | 2018-10-29 | 2019-01-29 | 宁波伏尔肯科技股份有限公司 | 一种高强度碳化硼多孔陶瓷的制备方法 |
CN111153712A (zh) * | 2019-12-31 | 2020-05-15 | 南京即衡科技发展有限公司 | 一种多孔陶瓷互穿网络中子屏蔽复合材料及其制备方法 |
-
2021
- 2021-10-29 CN CN202111268562.0A patent/CN113999043A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3153636A (en) * | 1958-10-31 | 1964-10-20 | Carborundum Co | Porous bodies of controlled densities and methods of making them |
CN102757223A (zh) * | 2012-07-04 | 2012-10-31 | 山东大学 | 一种稀土硼化物/碳化硼复合中子吸收材料及其制备方法 |
CN104311136A (zh) * | 2014-10-22 | 2015-01-28 | 山东理工大学 | 一种氮化硅、碳化硅结合碳化硼泡沫陶瓷的制备方法 |
CN106699185A (zh) * | 2016-11-30 | 2017-05-24 | 潘云清 | 一种铝合金复合材料 |
CN108863442A (zh) * | 2018-06-13 | 2018-11-23 | 南京航空航天大学 | 一种中子屏蔽复合材料及其制备方法 |
CN109279909A (zh) * | 2018-10-29 | 2019-01-29 | 宁波伏尔肯科技股份有限公司 | 一种高强度碳化硼多孔陶瓷的制备方法 |
CN111153712A (zh) * | 2019-12-31 | 2020-05-15 | 南京即衡科技发展有限公司 | 一种多孔陶瓷互穿网络中子屏蔽复合材料及其制备方法 |
Non-Patent Citations (1)
Title |
---|
陈茂开等: "烧结温度对SiC/莫来石复相多孔陶瓷的影响", 《材料导报B:研究篇》 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114621024A (zh) * | 2022-03-23 | 2022-06-14 | 山东华屹科创纳米材料有限公司 | 一种高纯增韧碳化硼泡沫陶瓷及其制备方法 |
CN114920564A (zh) * | 2022-05-07 | 2022-08-19 | 刘峻廷 | 一种高纯碳化硼管式陶瓷过滤膜制备方法 |
CN115745638A (zh) * | 2022-12-08 | 2023-03-07 | 武汉科技大学 | 一种莫来石-碳化硼轻质耐火材料及其制备方法 |
CN115745638B (zh) * | 2022-12-08 | 2023-06-06 | 武汉科技大学 | 一种莫来石-碳化硼轻质耐火材料及其制备方法 |
CN115959909A (zh) * | 2022-12-09 | 2023-04-14 | 武汉科技大学 | 一种B4C-莫来石-NbB2复合陶瓷及其制备方法 |
CN115959909B (zh) * | 2022-12-09 | 2023-08-22 | 武汉科技大学 | 一种B4C-莫来石-NbB2复合陶瓷及其制备方法 |
CN116178895A (zh) * | 2023-02-21 | 2023-05-30 | 哈尔滨理工大学 | 一种高导热环氧树脂复合材料及其制备方法和应用 |
CN116178895B (zh) * | 2023-02-21 | 2024-01-23 | 哈尔滨理工大学 | 一种高导热环氧树脂复合材料及其制备方法和应用 |
CN116749413A (zh) * | 2023-08-22 | 2023-09-15 | 中核北方核燃料元件有限公司 | 一种耐高温复合屏蔽材料及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113999043A (zh) | 一种互穿型莫来石/碳化硼泡沫陶瓷耐高温中子屏蔽材料及其制备方法 | |
CN108335760B (zh) | 一种高铀装载量弥散燃料芯块的制备方法 | |
CN106866151B (zh) | 一种浆料注射工艺制备碳纤维增韧硼化锆-碳化硅复合材料的方法 | |
CN106478105A (zh) | 一种多步反应烧结法制备低残硅的碳化硅陶瓷材料的方法 | |
CN106904984B (zh) | 一种SiC短纤维复合材料及复合包壳管及其制备方法 | |
CN102173813B (zh) | 一种含硼化锆复相陶瓷材料的制备方法 | |
WO2020042950A1 (zh) | 一种短纤维增强取向max相陶瓷基复合材料及制备方法 | |
CN107141004B (zh) | 一种碳化硼复合材料及其制备方法 | |
CN113666764B (zh) | 一种短切碳纤维增强碳化硅陶瓷复合材料墨水直写成型方法 | |
CN108484173B (zh) | SiCf/SiC复合材料及其制备方法 | |
CN106904977B (zh) | 一种两步烧结法制备表硬心韧Si3N4陶瓷材料的方法 | |
CN106278278B (zh) | 一种通过修饰前驱体来调控碳化硅热导率的方法 | |
CN113061036A (zh) | 一种复杂结构碳纤维-SiC晶须增强的SiSiC复合材料及制备方法 | |
CN104529499B (zh) | 一种自愈合碳化硅纤维增强硅硼氮碳复合材料的制备方法 | |
CN113666765A (zh) | 一种连续纤维增强高熵陶瓷基复合材料及其制备方法 | |
CN113121237A (zh) | 一种碳化硼基复合陶瓷及其制备工艺 | |
CN112794719A (zh) | 一种常压烧结抗辐照碳化硅陶瓷材料及其制备方法 | |
CN107746282B (zh) | 一种原位碳化硅纤维增强液相烧结碳化硅陶瓷及制造方法 | |
CN113735590B (zh) | 一种耐高温电磁吸波陶瓷基复合材料的制备方法及产品 | |
CN111892414A (zh) | 一种短碳纤维增强碳化硼复合材料及其制备方法 | |
CN104162661A (zh) | 一种Al2O3-TiC-TiN微米复合陶瓷刀具材料及其微波烧结方法 | |
CN111718208A (zh) | 一种陶瓷基复合材料用耐高温涂层的制备方法 | |
CN108484208B (zh) | 一种莫来石/刚玉基乏燃料贮运用中子屏蔽泡沫陶瓷及其制备方法 | |
CN113831102B (zh) | 连续玄武岩纤维增强磷酸基地质聚合物复合材料及其制备方法 | |
CN111153712A (zh) | 一种多孔陶瓷互穿网络中子屏蔽复合材料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220201 |
|
RJ01 | Rejection of invention patent application after publication |