CN117285307A - Preparation method of environment-friendly high-performance radiation-proof shielding concrete and product thereof - Google Patents
Preparation method of environment-friendly high-performance radiation-proof shielding concrete and product thereof Download PDFInfo
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- CN117285307A CN117285307A CN202311049809.9A CN202311049809A CN117285307A CN 117285307 A CN117285307 A CN 117285307A CN 202311049809 A CN202311049809 A CN 202311049809A CN 117285307 A CN117285307 A CN 117285307A
- Authority
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- Prior art keywords
- concrete
- radiation
- fine aggregate
- proof
- crt glass
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- 239000004567 concrete Substances 0.000 title claims abstract description 269
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 110
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000002699 waste material Substances 0.000 claims abstract description 54
- 230000005855 radiation Effects 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000011282 treatment Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- 239000004576 sand Substances 0.000 claims abstract description 20
- 238000005728 strengthening Methods 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000004575 stone Substances 0.000 claims abstract description 12
- 238000000280 densification Methods 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 33
- 239000002893 slag Substances 0.000 claims description 32
- 238000012360 testing method Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000004568 cement Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 21
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000012615 aggregate Substances 0.000 description 127
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 229910001385 heavy metal Inorganic materials 0.000 description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 description 18
- 239000011707 mineral Substances 0.000 description 18
- 238000002386 leaching Methods 0.000 description 12
- 239000011133 lead Substances 0.000 description 11
- 230000003471 anti-radiation Effects 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000010802 sludge Substances 0.000 description 9
- 230000002285 radioactive effect Effects 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 7
- 230000000740 bleeding effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 230000005251 gamma ray Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000010428 baryte Substances 0.000 description 4
- 229910052601 baryte Inorganic materials 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 238000005025 nuclear technology Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000010922 glass waste Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 238000000084 gamma-ray spectrum Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000002683 reaction inhibitor Substances 0.000 description 2
- 239000011376 self-consolidating concrete Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 201000004384 Alopecia Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 206010000210 abortion Diseases 0.000 description 1
- 231100000176 abortion Toxicity 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 cadmium metals Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000001465 calcium Nutrition 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 208000024963 hair loss Diseases 0.000 description 1
- 230000003676 hair loss Effects 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 208000000509 infertility Diseases 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 231100000535 infertility Toxicity 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 201000002364 leukopenia Diseases 0.000 description 1
- 231100001022 leukopenia Toxicity 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000011418 maintenance treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 231100000075 skin burn Toxicity 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000006016 thyroid dysfunction Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- 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
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/022—Carbon
- C04B14/024—Graphite
-
- 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
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/22—Glass ; Devitrified glass
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/12—Multiple coating or impregnating
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0231—Carbon dioxide hardening
-
- 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
-
- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00862—Uses not provided for elsewhere in C04B2111/00 for nuclear applications, e.g. ray-absorbing concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a preparation method of environment-friendly high-performance radiation-proof shielding concrete, which comprises the steps of grinding waste Cathode Ray Tube (CRT) glass crushing balls into CRT glass powder fine aggregate; immersing the waste CRT glass powder fine aggregate in a chemical packaging solution for surface strengthening treatment; mixing the surface-reinforced waste CRT glass powder fine aggregate, river sand fine aggregate, broken stone coarse aggregate, cementing material, graphene, water and high-efficiency water reducing agent to obtain fresh radiation-proof concrete; after demolding the freshly mixed radiation-proof concrete, performing surface densification treatment in a carbon dioxide environment to prepare the environment-friendly high-performance CRT glass radiation-proof shielding concrete. The invention realizes recycling and recycling of waste, and the prepared radiation-proof shielding concrete has better working performance, mechanical property, radiation shielding effect and lower permeability than the traditional radiation-proof shielding concrete, has wide application field and can generate good technical, economic, social and environmental protection benefits.
Description
Technical Field
The invention relates to a preparation method of environment-friendly high-performance radiation-proof shielding concrete and a product thereof, belonging to the field of industrial waste recycling and radiation-proof shielding material preparation.
Background
With the progress of industrial civilization in the world, environmental problems caused by traditional energy sources such as coal, petroleum and the like have become a worldwide concern. Under the general trend of continuously advancing low-carbon economy worldwide, the nuclear power technology is taken as a novel, clean and high-efficiency source, and is valued by all countries of the world since birth. By 2010, the final assembly machine of the nuclear power building unit in China reaches 2540 kilowatts and accounts for 40% of the total world nuclear power, and the final assembly machine becomes the country with the largest nuclear power building standard in the world. With the continuous enhancement of health consciousness of people in modern society, the development of novel medical technology and the continuous emergence of novel treatment means, nuclear technology is increasingly widely applied in the field of medical science research. Nuclear technology also plays a more important role in military, agriculture, exploration, etc.
The human enjoys the nuclear technology to bring great economic and social benefits, and the nuclear safety is also regarded as a key factor for restricting the development of the nuclear technology. The nuclear facilities and nuclear equipment can generate radioactive rays in the actual operation process, skin burn, hair loss and leukopenia can occur after long-time exposure to the radioactive rays, and malignant tumors, thyroid dysfunction, infertility, abortion and fertility defects can even be caused. Under the irradiation of long-term radioactive rays, genes can be mutated to endanger the growth of crops, the latent period of the radioactive rays on the crops is long, and the damage of the crops cannot be known in a short time. The radiation sources in nuclear and medical equipment are subject to fission, decay to produce fission fragments and release higher energy, which causes the instrument materials to heat and reduce the usability of the measuring instrument. How to effectively shield radioactive radiation in nuclear facilities, reduce the influence of radiation rays on the surrounding environment, and protect the health of staff has become an important point of attention in countries around the world.
The radiation-proof shielding materials commonly used at present comprise lead plates, steel plates, water and radiation-proof concrete. The lead material has better shielding performance on radioactive rays, but has a 'blind area' on rays with specific energy sections. The lead metal has less source and high engineering application cost. In addition, the creep of the lead material is large, so that the lead material is not suitable for being applied to members with large load and large bearing capacity; when the steel plate is used as a radiation-proof material, the mechanical property is good, but the construction performance is poor, the corrosion is easy, and the like; although the water can effectively protect neutron rays and has low cost, the required thickness is larger, the protective layer structure is difficult to shape, and the structure treatment, subsequent maintenance and management are complex; the radiation-proof concrete has the advantages of lower material cost, convenient construction, capability of being built into structures of any size and shape, good protective performance, capability of being used as a support of the structure and the like, and is the most widely used radiation-proof material at present in terms of technology, economy, effect and the like. Today, radiation-proof concrete has been applied to nuclear reactor containment vessels, military nuclear facility enclosures, and protection of educational, scientific, medical facility radiation source enclosures and nuclear waste storage facilities, playing an important role in shielding radiation and protecting nuclear equipment from safe use.
The radiation types in nuclear radiation are many, wherein alpha, beta, χ, gamma and neutron rays have the greatest damage to human bodies. The radiation penetration energy of the alpha rays and the beta rays is small, the alpha rays and the beta rays are easy to absorb, and the rays can be shielded by the protective material with small thickness. The X and gamma rays are high-frequency and high-energy electromagnetic waves, most of energy is lost due to Compton scattering effect when the X and gamma rays pass through the high-density concrete material, so that the intensity of the X and gamma rays is reduced, and the X and gamma rays can be completely absorbed when the radiation-proof concrete reaches a certain density and thickness. Neutron rays are particle flows composed of neutral particles, and the penetration capacity of the neutron rays is far stronger than that of χ and γ rays. Neutron rays can be divided into fast neutrons, medium-speed neutrons and slow neutrons according to the radiation capacity, and the shielding mechanisms of different types of neutron rays are different. When fast neutrons collide with heavy atomic nuclei, the fast neutrons generate elastic and inelastic scattering loss energy, and the fast neutrons can be absorbed or captured by related substances after being reduced into slow neutrons, so that the shielding deceleration effect can be achieved. The shielding of medium and slow neutrons can be achieved by adding light element absorbers of hydrogen, boron, lithium, cadmium, etc. In the process of preparing the radiation-proof concrete, the strength, apparent density and compactness of the concrete are improved, and the porosity of the concrete is reduced, so that the protective capability of the radiation-proof concrete can be effectively improved. Meanwhile, the contents of heavy atomic nucleus elements, light elements and cement hydration product crystal water in the concrete are directly related to the radiation shielding effect of the concrete on the neutron rays.
The radiation-proof shielding concrete is similar to common concrete material in composition and is prepared with cement, mineral admixture, fine aggregate, coarse aggregate, water and chemical additive in certain proportion. In the preparation process of the radiation-proof shielding concrete, the introduction of light element compounds containing boron and lithium and crystal water is the most common method for preparing the radiation-proof concrete. The mineral admixture is added to reduce the water-cement ratio of concrete, reduce the shrinkage rate of concrete and improve the cracking resistance, the compactness and the radiation shielding capability of concrete. The mixing of barite, limonite, hematite, magnetite, barite, serpentine, olivine and steel sand as coarse and fine aggregates is the key for preparing high-performance radiation-proof shielding concrete. However, the mineral admixture in the existing radiation-proof shielding concrete contains less hydrogen, boron, lithium and cadmium light elements, the light elements are mainly realized by doping light element additives and fine aggregates, and the mineral admixture has limited effect on improving the shielding effect of the radiation-proof concrete; although the apparent density and shielding effect of the concrete can be improved by the iron heavy aggregate and the natural heavy aggregate, the iron heavy aggregate and the natural heavy aggregate have low crystalline water content and poor neutron protection capability, and the iron heavy aggregate can generate strong secondary gamma rays under the neutron action; the apparent density of iron and natural heavy aggregate is larger than that of cement paste, uniformity of fresh radiation-proof concrete cannot be guaranteed, uneven shrinkage can occur in the hardening process of the concrete, and cracking and shielding performance of the concrete are reduced; the radiation-proof concrete prepared from the heavy aggregate also increases the dead weight of the building and brings adverse effects to the earthquake resistance of the nuclear building; the strength of the heavy aggregate is generally lower, the strength of the heavy aggregate radiation-proof concrete is lower than that of common concrete, and the heavy aggregate concrete cannot be used for bearing members in nuclear facilities. Therefore, the research on the modern radiation-proof shielding concrete with wide sources and higher radiation shielding effect on the radiation is carried out by searching other mineral admixtures which are wide in sources and have higher radiation shielding effect on the radiation, adopting the novel lightweight aggregate to replace the common heavy aggregate, and having good workability, volume stability, high crystal water content in the hardened concrete and good mechanical property and radiation shielding effect is a research hot spot problem in the field at home and abroad.
At present, the comprehensive utilization rate of copper slag is low, and a large amount of copper slag waste is buried without treatment. Chemical analysis of the copper slag shows that SiO in the steel slag 2 、Fe 2 O 3 、CaO、MgO、Al 2 O 3 The weight ratio of the slag is 8-23%,15-26%,30-60%,4-11%,3-8%, the slag contains minerals such as tricalcium silicate, dicalcium silicate, calcium forsterite, calcium magnesium rosepside, dicalcium ferrite, free calcium oxide and free magnesium oxide, the vitreous component is up to 85%, the slag has high volcanic ash activity, and the ground copper slag powder can be used as mineral admixture to prepare radiation-proof shielding concrete. The finely ground copper slag mineral admixture also contains copper, lead, zinc, arsenic metal and crystal water, and has good shielding effect on rays. The ground copper slag powder has smaller particle size and compact structure, and can optimize the particle size distribution of fine particles in the concrete when being used as mineral admixture to be doped into the concrete, so that the gaps of the concrete are effectively filled, a compact net structure is formed, and the radiation-proof shielding mechanical property of the concrete is improved.
Previous researches show that the light aggregate prepared from industrial wastes can replace common iron heavy aggregate and natural heavy aggregate to prepare the radiation-proof shielding concrete. Huang Xiulin (research on preparing radiation-proof functional aggregate and concrete thereof by heavy metal-containing sludge, university of martial arts, doctor's school paper, 2011) uses heavy metal-containing sludge aggregate to prepare radiation-proof shielding concrete, and the system researches the influence rule of mineral composition, roasting temperature and roasting time of heavy metal-containing sludge on physical mechanical property, microstructure and shielding property of sludge functional aggregate, and establishes the relationship among concrete composition, pore structure and radiation-proof shielding property. By utilizing microscopic analysis means such as XRD, SEM, microhardness, MPI and the like, the hardening mechanism, microstructure and interface characteristic of the radiation-proof shielding concrete are systematically researched, and the mechanism of excellent physical and mechanical properties, cracking resistance, durability and shielding property of the radiation-proof shielding concrete is explained. But the sludge containing heavy metals has wide sources, complex mineral composition and structure of the sludge, large water content of the sludge, and large fluctuation of physical and mechanical properties and heavy metal content of the sludge. When the proportion of the heavy metal-containing sludge functional aggregate to replace the iron heavy aggregate and the natural heavy aggregate is too large, the flowability and mechanical property of the radiation-proof shielding concrete can be obviously reduced. In recent decades, with the increasing progress of display technology, a large number of cathode ray tubes have entered a discard stage, creating excessive Cathode Ray Tube (CRT) electronic waste. Cathode ray tube glass is an important component of cathode ray tubes. The cathode ray tube glass contains silicate glass and heavy metal lead, the doped and crushed waste cathode ray tube glass is used for the radiation-proof shielding concrete instead of the traditional heavy aggregate, and the high-content PbO in the cathode ray tube glass aggregate has strong absorption and reflection effects on gamma rays and neutrons, can effectively shield rays, and opens up a new direction for preparing the high-performance radiation-proof concrete. Wang Can (influence of CRT waste glass fine aggregate on the performance of the heavy-rock radiation-proof concrete, university of south China, university of major, university of Chinese academic paper, 2020) shows that as the mixing amount of waste CRT glass fine aggregate increases, the slump, slump expansion and apparent density of the self-compaction radiation-proof concrete increase, and the V-shaped funnel passing time and T500 expansion time decrease. The addition of the waste CRT glass fine aggregate obviously improves the compressive strength, the splitting tensile strength, the axial compressive strength and the elastic modulus of the self-compacting anti-radiation concrete, and the CRT glass fine aggregate can also effectively increase the gamma-ray absorption coefficient of the anti-radiation self-compacting concrete and reduce the gamma-ray half-attenuation layer thickness and ten times of attenuation thickness. However, the mechanical property and the radiation-proof shielding property of the self-compacting concrete can be slightly reduced by excessively increasing the mixing amount of the waste CRT glass micro aggregate, and the thickness of the gamma-ray half-attenuation layer and the ten-fold attenuation thickness of the concrete are kept between 0.03 cm and 0.08 cm. The waste CRT glass fine aggregate is added into the radiation-proof concrete, active silicon dioxide in the CRT glass can react with alkaline substances in the concrete to generate alkali-silicate gel, and the alkali-silicate gel in the material swells in volume after absorbing water, so that the radiation-proof concrete swells, the volume stability is poor and the long-term performance is deteriorated. In order to improve the durability of the radiation-proof concrete material, the doping amount of the CRT glass fine aggregate is generally controlled to be about 30 percent, which influences the radiation shielding effect of the radiation-proof concrete and restricts the wide application of CRT glass waste in the radiation-proof concrete. When the radiation-proof concrete is prepared, the heavy metals of lead, zinc, nickel and cadmium in the CRT glass aggregate have the effect of shielding rays, but in the preparation and long-term use process of the radiation-proof concrete, the toxic heavy metals can penetrate into the environment to pollute the soil and water around nuclear facilities, and influence the growth of animals and plants and the physical health of people. The method for preparing the cathode ray tube glass radiation-proof shielding concrete is environment-friendly, and is focused by researchers in various countries, so that a constructive thought is provided for effectively solving the problem of environmental pollution caused by toxic heavy metals in the CRT glass and improving the radiation-proof effect of the concrete.
Disclosure of Invention
The invention aims to: the invention is based on improving the contribution of mineral admixture to the shielding effect of the radiation-proof concrete, improving the compactness of the CRT glass fine aggregate and the cement paste, reducing the negative influence on the volume stability and the mechanical property of the radiation-proof concrete caused by alkali-silicate reaction of the CRT glass fine aggregate, and improving the consideration of the aspects of the compatibility of the CRT glass radiation-proof concrete and the environment. Cement and ground copper slag powder are used as cementing materials, graphene and surface-reinforced CRT glass fine aggregate are doped into the anti-radiation shielding concrete, and the anti-radiation shielding concrete is subjected to surface densification maintenance treatment to prepare the environment-friendly high-performance waste CRT glass anti-radiation shielding concrete.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a method for preparing an environment-friendly, high-performance radiation-proof shielding concrete, comprising the steps of:
(1) Crushing and ball-milling the waste CRT glass into waste CRT glass powder fine aggregate with certain particle size distribution, immersing the waste CRT glass powder fine aggregate in a chemical packaging solution for surface strengthening treatment, and covering a layer of polymer film on the surface of the waste CRT glass powder fine aggregate;
(2) Mixing the surface-reinforced waste CRT glass powder fine aggregate, river sand fine aggregate, broken stone coarse aggregate, cementing material, graphene, water and high-efficiency water reducer in proportion to obtain fresh radiation-proof concrete;
(3) And demolding the newly mixed radiation-proof concrete, and placing the newly mixed radiation-proof concrete into a carbon dioxide environment for surface densification treatment to prepare the environment-friendly high-performance CRT glass radiation-proof shielding concrete.
Wherein, sodium hexametaphosphate is used as a grinding aid in the step (1), and the grinding aid is 3% of the weight of the waste CRT glass powder fine aggregate. The grinding speed of the waste CRT glass powder fine aggregate is 800 revolutions per minute, and the grinding time is 5-10 minutes. The size of the waste CRT glass powder fine aggregate is controlled to be 3.7-3.8 mu m.
Wherein the chemical packaging solution in the step (1) is guar gum aqueous solution, the weight ratio of the waste CRT glass powder fine aggregate to the chemical packaging solution is 1:2.0-1:2.1, the strengthening temperature of the CRT glass powder fine aggregate is 35-40 ℃, and the strengthening time is 1.5-2 hours.
Wherein in the step (2), the ratio of the fine aggregate to the coarse aggregate to the cementing material to the water is 4.31:6.74:2.86:1, the cementing material comprises cement and finely ground copper slag powder, and the finely ground copper slag powder accounts for 25-30% of the total weight of the cementing material. The graphene accounts for 3% of the total amount of the cementing material. The fine aggregates are surface-reinforced CRT glass powder fine aggregates and river sand fine aggregates, and the mass ratio of the surface-reinforced CRT glass powder fine aggregates to the river sand fine aggregates is 6:4. the high-efficiency water reducing agent of the polycarboxylic acid is 0.12 percent of the total amount of the cementing material.
Wherein, the fresh radiation-proof concrete in the step (2) is prepared from the following components in parts by weight: 320-325 parts of cement, 135-140 parts of ground copper slag powder, 13.5-14 parts of graphene, 415-420 parts of river sand fine aggregate, 275-280 parts of reinforced waste CRT glass powder fine aggregate, 1085-1090 parts of crushed stone coarse aggregate and 160-165 parts of mixed water doped with a polycarboxylic acid high-efficiency water reducer.
Wherein, the step (3) comprises the following preparation steps: and (3) mixing fresh concrete slurry in an acceleration way, respectively pouring fresh concrete into test molds to prepare samples, covering the concrete test molds with wet gunny bags, placing the concrete test molds in a room with the temperature of 25 ℃ and the humidity of 55-65%, removing the concrete test molds after 24 hours, and transferring the concrete test specimens into a standard carbonization environment to be cured to a specified age.
Wherein the test die comprises 100mm×100mm, 150mm×150mm×550mm, 100mm×100mm×300mm, phi 40mm×80mm.
Wherein the standard carbonization environment is CO 2 The concentration is 2+/-0.5%, the temperature is 20+/-5% and the humidity is 70+/-5%.
The invention also discloses the environment-friendly high-performance radiation-proof shielding concrete prepared by the method, which is used for measuring the compressive strength, flexural strength, radiation-proof performance and heavy metal leaching amount of the hardened radiation-proof shielding concrete in a specified age.
Reaction mechanism: strengthening waste Cathode Ray Tube (CRT) glass; the CRT glass anti-radiation shielding concrete is prepared by using ground copper slag powder, graphene and reinforced CRT glass fine aggregate to prepare concrete and carrying out surface densification treatment on the concrete. The method for preparing the radiation-proof concrete has the advantages that the ground copper slag powder is used as the auxiliary cementing material, the influence of cement usage in the concrete and the discharge of CO2 isothermal chamber gas and industrial dust in the cement production process on the environment is reduced, and the mineral admixture contribution to the shielding effect of the radiation-proof concrete is improved by adding the ground copper slag powder auxiliary cementing material. The mixing of the graphene improves the cohesiveness of the fine aggregate and the cement paste in the radiation-proof concrete and reduces the void ratio of the concrete. The waste Cathode Ray Tube (CRT) glass fine aggregate replaces iron heavy aggregate and natural heavy aggregate to prepare the radiation-proof concrete, so that a great deal of cathode ray tube glass waste is consumed, the problems that a great deal of land is occupied and serious pollution is caused to surrounding environment is caused when the solid cathode ray tube waste is treated by a traditional landfill method are avoided, the surface strengthening treatment is carried out on the CRT glass fine aggregate, the leaching rate of toxic lead, zinc, nickel and cadmium metals in the CRT glass fine aggregate from the concrete is reduced, the contact of active silicon dioxide in the CRT glass fine aggregate and hydrated alkaline substances is avoided when the concrete is subjected to surface densification treatment, the possibility of alkali-silicate reaction is reduced, and the volume stability of the concrete is improved. The radiation-proof shielding concrete prepared by the method realizes recycling and recycling of wastes, has better working performance, mechanical property, radiation shielding effect and lower permeability than the traditional radiation-proof shielding concrete, has wide application field, and can generate good technical, economic, social and environmental benefits.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The radiation-proof shielding concrete is prepared by using the finely ground copper slag powder mineral admixture, the proportion of the finely ground copper slag powder mineral admixture to replace cement is up to 30 percent, and compared with the radiation-proof shielding concrete which commonly uses the fly ash mineral admixture, the radiation-proof shielding concrete can save the cost of the mineral admixture by up to 6.29 yuan per cubic meter of production.
(2) The waste CRT glass powder fine aggregate can completely replace iron heavy aggregate and natural heavy aggregate, can obviously improve the mechanical property and radiation-proof shielding property of the radiation-proof shielding concrete, and can produce economic benefit of more than 3.12 yuan per cubic meter of the radiation-proof shielding concrete.
(3) The graphene is doped into the fresh radiation-proof concrete, so that the workability of cement paste is improved, the consumption of related concrete additives is reduced, the compactness of the CRT glass fine aggregate radiation-proof concrete is improved, and the consumption of the concrete additives can be reduced by 0.89 yuan per cubic meter of the radiation-proof shielding concrete produced.
(4) The radiation-proof concrete is subjected to carbon dioxide surface densification curing treatment, so that the addition of alkali silicate reaction inhibitor in a concrete material is reduced, the prepared radiation-proof concrete has lower alkali silicate reaction expansion and good volume stability, and the cost of the alkali silicate reaction inhibitor can be saved by 1.54 yuan.
(5) The radiation-proof shielding concrete prepared by grinding the copper slag powder with the solid waste reduces the influence of CO2 greenhouse gas emission and industrial dust emission on the environment in the cement production process.
(6) The waste CRT glass powder is used as fine aggregate to consume a large amount of waste CRT glass, so that the problems that the waste CRT glass needs to occupy a large amount of land and serious pollution is caused to the surrounding environment in the conventional landfill method are avoided.
(7) The CRT glass powder fine aggregate is strengthened, so that toxic heavy metal exudation in radiation-proof shielding concrete is reduced, the application field and range of waste cathode ray tube glass are enlarged, and a new way is found for recycling the cathode ray tube glass waste.
Considering all, according to the preparation method of example 1, the 10-square method for producing the environment-friendly and high-performance radiation-proof shielding concrete every year can produce 118.4-ten thousand-yuan economic benefit.
Drawings
FIG. 1 is a flow chart for preparing an environmentally friendly, high performance radiation protective shielding concrete;
FIG. 2 is an illustration of three green radiation shield concretes initial slump flow and slump flow retention;
FIG. 3 shows the bleeding rates of three fresh radiation-protected concretes;
FIG. 4 is a graph of wet densities of three fresh radiation-shielding concretes;
FIG. 5 is a graph showing the change of the compressive strength of three radiation-proof shielding concretes with curing time;
FIG. 6 is a graph showing the flexural strength of three radiation-protective shielding concretes as a function of curing time;
FIG. 7 is a graph of the radiation shielding performance of three radiation shielding concretes;
fig. 8 shows the leaching amounts of heavy metals from three radiation-protective shield concretes.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
The environment-friendly high-performance radiation-proof shielding concrete with one cubic meter prepared by the invention is mixed with undoped graphene and is not subjected to CO under the same mixing ratio 2 The properties of the radiation-shielding concrete samples of the surface densified heavy-crystal stone fine aggregate and the non-surface-reinforced CRT glass fine aggregate were compared.
1. Preparation of finely ground waste cathode ray tube fine aggregate
Sorting, cleaning and airing 860kg of waste cathode ray tube glass (from hong Kong solid waste recycling center), crushing, putting the crushed waste cathode ray tube glass into a vibrating ball mill, adding 25.5kg of sodium hexametaphosphate (manufactured by Shandong Kai Mi Ke New Material Co., ltd.) grinding aid into the ball mill, grinding for 5-10 minutes at 800 rpm, passing the ball-milled waste cathode ray tube glass through a 0.60mm round hole sieve, and retaining waste cathode ray tube glass fine particles with the particle size smaller than 0.60 mm. After the ground cathode-ray tube glass frit was hermetically left for 24 hours, 856.7kg of a waste cathode-ray tube glass frit fine aggregate was obtained, and the average particle size of the ground cathode-ray tube glass frit fine aggregate was 3.783 μm as measured by using a laser particle sizer.
2. Strengthening treatment of finely ground waste cathode ray tube fine aggregate
850kg of the finely ground CRT glass frit fine aggregate was immersed in 1700kg of 0.1 wt% guar gum aqueous solution (industrial grade, shanghai Li and manufactured by Sci Co., ltd.) for reinforcement treatment at 35℃for 2 hours with continuous stirring, so that the surface of the waste CRT glass frit fine aggregate was covered with a polymer film. And (3) airing the surface-reinforced finely ground cathode ray tube glass powder fine aggregate, further ball-milling for 5 minutes in a vibrating ball mill, and then passing through a 0.6mm round hole sieve to obtain the surface-reinforced finely ground cathode ray tube glass powder fine aggregate for later use.
3. Preparation of radiation-proof shielding concrete doped with reinforced and ground waste cathode-ray tube glass powder fine aggregate
3.1. Radiation-proof shielding concrete mixing proportion
The preparation of C50 radiation-proof shielding concrete with 28d strength reaching 50MPa is aimed. Cement and ground copper slag powder are used as cementing materials. The cement is 42.5 ordinary silicon cement produced by China cement plant Co., ltd, and the ground copper slag powder is copper slag powder of copper slag flotation tailings of Guixi smeltery in Jiangxi province. The grain size of the ground copper slag powder is smaller than 0.074mm and accounts for 94.80%, and the ground copper slag powder mainly comprises SiO 2 f-CaO, mgO, caO.Fe 2 O 3 MgO.3FeO, anorthite (CaAl) 2 Si 2 O 8 ) Lime garnet (Ca) 3 Fe 2 (SiO 4 ) 3 ) Mineral composition, further comprising 0.35% metallic copper, 0.21% metallic lead, 1.69% metallic zinc. Graphene (technical grade) is produced by Ningbo ink technologies Inc. The natural fine aggregate is Jiangsu Nanjing outer Qinhuai river sand, the grain diameter is smaller than 5mm, and the fineness modulus of the fine aggregate is 2.46. The surface-reinforced ground cathode ray tube glass powder prepared in the step 2 is used as a fine aggregate for preparing radiation-proof shielding concrete, industrial-grade barite sand fine aggregate produced by barite Limited liability company, anchu, shandong province, and the non-surface-reinforced CRT glass powder prepared in the step 1 is used as a comparison fine aggregate. The fineness modulus of the three fine aggregates is 2.78,1.24,1.56, and the absolute dry density is 3043.9kg/m 3 ，4401.8kg/m 3 ，3064.1kg/m 3 The CRT glass fine aggregate prepared in the step 1 contains 376.1g/L lead oxide. The coarse aggregate is 5-25mm continuous graded broken stone of Anhui and county. The high-efficiency water reducer is a polycarboxylic acid high-efficiency water reducer (PCE) produced by Jiangsu construction science institute, and the solid content of the PCE high-efficiency water reducer is 20%. The mixing water is drinking water. The proportion of the radiation-proof shielding concrete is cementing material (cement and ground copper slag powder): fine aggregate (river sand + heavy-grain stone sand; or river sand + non-surface-strengthened CRT glass frit; or river sand + surface-strengthened CRT glass frit): coarse aggregate: water = 1:1.51:2.36:0.35 (weight ratio). The total amount of cementing materials in the radiation-proof shielding concrete of one cubic meter is 460kg/m 3 The ground copper slag powder is 30% of the total amount of the cementing material, and the proportion of the heavy crystal stone sand, the CRT glass powder without surface reinforcement and the CRT glass powder fine aggregate with surface reinforcement to replace river sand fine aggregate is 40%. The dosage of the graphene is 3% of the total amount of the cementing material. High efficiency of polycarboxylic acidThe water reducer accounts for 0.12 percent of the total amount of the cementing material. The proportion of the three groups of C50 radiation-proof shielding concrete is shown in Table 1, and the radiation-proof shielding concrete (BARITE-C50) doped with heavy-duty stone sand and the CRT glass powder radiation-proof shielding concrete (NCRT-C50) which is not surface-reinforced are used as comparison samples.
TABLE 1 three groups of C50 radiation-proof shielding concrete mix proportion
3.2. Preparation and maintenance of radiation-proof shielding concrete
322kg of cement, 138kg of ground copper slag powder and 13.8kg of graphene are put into a stirrer and mixed for 2 minutes at a stirring speed of 30 revolutions per minute, and then 416.3kg of river sand, 277.52kg of waste CRT glass powder after strengthening treatment and 1085.2kg of crushed stone are added and mixed for 2 minutes at a stirring speed of 30 revolutions per minute. Finally, 161kg of mixing water doped with the polycarboxylic acid high-efficiency water reducer is added into a container, stirring is continued for 2 minutes at a stirring speed of 30 revolutions per minute, and in order to avoid layering of fresh concrete slurry at the bottom of the container, a shovel is required to be used for manually stirring the fresh concrete slurry for 1-2 times, and the fresh concrete slurry is accelerated to be stirred for 2 minutes at a stirring speed of 60 revolutions per minute. And taking a small amount of fresh CRT-C50 concrete for detecting the initial fluidity, fluidity retention, workability and wet density performance. And pouring part of fresh CRT-C50 concrete into 100mm multiplied by 150mm multiplied by 550mm moulds respectively to prepare 24 samples, and detecting the compressive strength and the flexural strength of the 3,7, 28 and 90d concrete. And pouring the other parts of fresh concrete slurry into a 100mm multiplied by 300mm mould, preparing 3 samples, and detecting the radiation shielding performance of 28d concrete. The rest fresh CRT-C50 concrete slurry is poured into a mould with phi of 40mm multiplied by 80mm for 28d of cured concrete heavy metal leaching amount detection. Finally, the CRT-C50 concrete test mold is covered by a wet gunny bag, placed in a room with the temperature of 25 ℃ and the humidity of 55-65%, and after 24 hours, the mold is removed, and the concrete test piece is transferred to a standard Carbonization (CO) 2 The concentration is 2+/-0.5%, the temperature is 20+/-5%, and the humidity is 70+/-5%) in the environment for curing to the specified age. Preparation of the same quantity of comparative BARITE-And C50 and NCRT-C50 radiation-proof shielding concrete samples are placed in a standard curing room with the temperature of 20 ℃ and the humidity of 90+/-5% for curing to the testing age, and a comparison experiment is carried out.
3.3. Method for testing radiation-proof shielding concrete
3.3.1. Initial fluidity and fluidity retention of fresh concrete
The cone slump test cartridges were wiped clean with a wet cloth and placed on a horizontally placed steel plate. The freshly mixed concrete was loaded into slump test barrels in three layers, and the concrete was uniformly inserted and rammed 25 times from edge to center using a vibrating bar after each layer of test material was loaded. After the concrete is fully tamped, the surface of the concrete is smoothed, the slump cone is lifted slightly and vertically, the flow of the fresh concrete is stopped, and the average value of the concrete mixture in two directions perpendicular to each other is measured to be used as the initial slump flow of the fresh concrete. To determine the retention of concrete fluidity, after the initial slump flow test of concrete was completed, concrete samples were placed in an iron drum and allowed to stand for 30, 60, 90, 120 minutes, and the slump flow was repeatedly determined for a prescribed period of time. The concrete sample is re-stirred before each slump flow test.
Fig. 2 shows the initial slump flow and slump flow retention of three fresh radiation protected concretes. As can be seen from the view of figure 2, the two CRT glass fine aggregate radiation protection concretes have higher initial slump fluidity than the fine aggregate radiation protection concretes of the specific boulder, the addition of the graphene slightly reduces the initial slump fluidity of the CRT glass fine aggregate radiation-proof shielding concrete subjected to the fresh surface strengthening treatment. Meanwhile, as the placing time is increased, the slump fluidity of the three newly mixed radiation-proof shielding concretes is reduced, the two CRT glass fine aggregate doped radiation-proof concretes have lower slump fluidity loss rate than that of the fine aggregate radiation-proof concrete, and the CRT glass fine aggregate is used for preparing the radiation-proof concrete, so that the concrete slump fluidity retention is better.
3.3.2. Workability of fresh concrete
The workability of the fresh concrete can be evaluated by using the bleeding rate index, the fresh concrete is filled into a container with a certain volume, the container filled with the fresh concrete is placed on a vibrating table to vibrate for 20 seconds, and the surface of the fresh concrete is gently smoothed by a spatula. Starting from the time of trowelling the surface, the water discharged from the concrete surface is sucked by a liquid suction pipe every 10 minutes in the first 60 minutes, and then sucked every 20 minutes until no water is discharged for three times continuously, and the accumulated amount of the discharged water in the fresh concrete is measured. The bleeding rate of the freshly mixed concrete is the weight percentage of the accumulated bleeding amount to the mixing water amount of the concrete.
FIG. 3 shows the bleeding rates of three fresh radiation-protective screen concretes. As can be seen from fig. 3, the two CRT glass aggregate radiation protection concretes have a higher bleeding rate than the fine aggregate radiation protection concretes of the specific weight of the fine aggregate, and the addition of the graphene slightly reduces the bleeding rate of the CRT glass aggregate concrete treated by the fresh surface strengthening treatment, thereby improving the workability of the fresh radiation protection shielding concretes.
3.3.3. Wet density of fresh concrete
The fresh concrete is put into a test container with a certain volume in three layers, and the concrete is vibrated and inserted 25 times after the fresh concrete is put into each time. After the concrete is filled and tamped, the surface of the freshly mixed concrete is smoothed and the excess concrete is removed. Weighing the weight of the fresh concrete in the test container and the volume of the test container, and defining the weight of the fresh concrete in the unit volume as the concrete wet density.
Fig. 4 shows the wet densities of three fresh radiation-protective shield concretes. As can be seen from the view of figure 4, two CRT glass fine aggregate radiation-proof concretes have specific gravity the radiation-proof concrete with fine aggregate of the boulder has lower wet density, the doping of the graphene slightly reduces the wet density of the CRT glass fine aggregate radiation-proof shielding concrete subjected to the fresh surface strengthening treatment.
3.3.4. Compressive strength of hardened concrete
The compressive strength of the concrete is tested according to national standard 'test method Standard for mechanical Properties of common concrete' (GB/T50081-2002), and in the curing age of 3,7, 28 and 90d, the compressive strength of the hardened concrete is tested by using a YAW-3000 electrohydraulic servo loading system, and the loading rate is 1.3MPa/s during the test.
Fig. 5 shows the change of the compressive strength of three radiation-proof shielding concretes with curing time. As can be seen from fig. 5. With the increase of the curing age, the compressive strength of the three radiation-proof shielding concretes is continuously increased. In the same curing period, the two types of CRT glass fine aggregate doped anti-radiation concrete have higher compressive strength than the fine aggregate anti-radiation concrete of the specific weight of the fine aggregate. Compared with the traditional CRT glass fine aggregate radiation-proof concrete, the graphene doping and carbon dioxide surface densification curing treatment increase the compactness and the volume stability of the concrete, and the CRT glass fine aggregate concrete doped with the surface strengthening treatment has higher compressive strength.
3.3.5. Flexural Strength of hardened concrete
The flexural strength of the concrete is tested according to the three-point flexural strength method of national standard of common concrete mechanical property test method (GB/T50081-2002). And in a specified age, placing the prism concrete sample molding surface upwards on a DYE-300 type full-automatic anti-breaking tester, and loading the side surface of the prism at a loading speed of 40N/s until the test piece breaks.
FIG. 6 shows the flexural strength of three radiation-protective, shielding concretes as a function of curing time. As can be seen from fig. 6. With the increase of the curing age, the flexural strength of the three radiation-proof shielding concretes is continuously increased. In the same curing period, the two types of CRT glass fine aggregate doped radiation-proof concrete have higher flexural strength than that of the fine aggregate radiation-proof concrete of the specific weight of the fine aggregate. Compared with the traditional CRT glass fine aggregate radiation-proof concrete, the graphene doping and carbon dioxide surface densification curing treatment increase the compactness and the volume stability of the concrete, and the CRT glass fine aggregate concrete doped with the surface strengthening treatment has higher flexural strength.
3.3.6. Radiation shielding properties of hardened concrete
After 28d of water curing, adopting 6150AD-5/H gamma-ray spectrum measuring instrument manufactured by AUTOMEGG, germany 137 Cs is taken as a radioactive source, the energy is 662 keV), the gamma-ray shielding performance of the anti-radiation concrete sample is tested, the distance between a gamma-ray spectrum measuring instrument and the radioactive source is 65cm, and the concrete sample is placed at a position 5cm away from the measuring instrument. Single energy gamma ray passing throughWhen the object is in use, part of gamma rays are absorbed by the substance, and other gamma rays passing through the concrete sample have certain attenuation in intensity. Along with the continuous increase of the thickness of the test piece, the intensity of the gamma rays passing through the test piece is weakened in an exponential manner. According to the difference of the gamma-ray absorption doses of the actual measured concrete, calculating the linear attenuation coefficient (mu) of the radiation-proof concrete according to the Langbey method, wherein the larger the mu is, the stronger the radiation-proof performance of the concrete is.
Fig. 7 shows the radiation-resistant shielding properties of three radiation-resistant shielding concretes. As can be seen from fig. 7, the two CRT glass fine aggregate doped radiation protective concretes have a higher linear attenuation coefficient and radiation shielding property than the fine aggregate radiation protective concretes. Compared with the traditional CRT glass fine aggregate radiation-proof concrete, the graphene doping and carbon dioxide surface densification curing treatment increase the compactness of the concrete, and the CRT glass fine aggregate concrete doped with the surface strengthening treatment has higher linear attenuation coefficient and radiation-proof shielding property.
3.3.7. Leaching amount of heavy metal in hardened concrete
In the invention, the leaching amount of heavy metals from hardened concrete is detected according to the method of horizontal oscillation method of solid waste leaching toxicity leaching method, HJ 557-2010. The cured concrete sample was crushed and ground for 28 days, and then passed through a 10mm round-hole sieve. Placing 5.0g concrete powder sample into extraction bottle, mixing with 100ml extract, adjusting pH of the extract to 2-3 with concentrated nitric acid or concentrated hydrochloric acid, fixing the extraction bottle on rotary extraction device, and continuously stirring at 30+ -2 rpm for extraction for 18 hr. After extraction, pouring the liquid in the extraction bottle into a quantitative bottle, quantifying to 100ml by using distilled water, filtering the dissolved liquid, and measuring the leaching concentration of the heavy metals of zinc, copper and lead in the hardened concrete by using a flame atomic absorption spectrometer.
Fig. 8 shows the leaching amounts of heavy metals from three radiation-protective shield concretes. As can be seen from fig. 8, the two CRT glass fine aggregate doped radiation protected concretes have lower zinc, copper and higher lead leaching concentrations than the fine aggregate radiation protected concretes. Compared with the traditional CRT glass fine aggregate radiation-proof concrete, the surface strengthening treatment is carried out on the CRT glass fine aggregate, so that the leaching concentration of heavy metals such as zinc, copper and lead from the concrete is further reduced.
Claims (10)
1. The preparation method of the environment-friendly high-performance radiation-proof shielding concrete is characterized by comprising the following steps of:
(1) Crushing and ball-milling the waste CRT glass into waste CRT glass powder fine aggregate with certain particle size distribution, immersing the waste CRT glass powder fine aggregate in a chemical packaging solution for surface strengthening treatment, and covering a layer of polymer film on the surface of the waste CRT glass powder fine aggregate to obtain the waste CRT glass powder fine aggregate subjected to the surface strengthening treatment;
(2) Mixing the surface-reinforced waste CRT glass powder fine aggregate, river sand fine aggregate, broken stone coarse aggregate, cementing material, graphene, water and high-efficiency water reducer to obtain fresh radiation-proof concrete;
(3) And demolding the newly mixed radiation-proof concrete, and placing the newly mixed radiation-proof concrete into a carbon dioxide environment for surface densification treatment to prepare the environment-friendly high-performance CRT glass radiation-proof shielding concrete.
2. The method for preparing environment-friendly and high-performance radiation-resistant shielding concrete according to claim 1, wherein the grinding aid used in the ball milling in the step (1) comprises sodium hexametaphosphate, wherein the sodium hexametaphosphate accounts for 3% of the weight of the waste CRT glass powder fine aggregate, the ball milling speed of the waste CRT glass powder fine aggregate in the step (1) is 800 revolutions per minute, the ball milling time is 5-10 minutes, and the size of the waste CRT glass powder fine aggregate obtained in the step (1) is controlled to be 3.7-3.8 mu m.
3. The method for preparing environment-friendly high-performance radiation-resistant shielding concrete according to claim 1, wherein the chemical packaging solution in the step (1) is guar gum water solution, the weight ratio of the waste CRT glass frit fine aggregate to the chemical packaging solution is 1:2.0-1:2.1, the strengthening temperature of the waste CRT glass frit fine aggregate in the step (1) is 35-40 ℃, and the strengthening time is 1.5-2 hours.
4. The method for preparing an environmentally friendly, high performance radiation protective shielding concrete according to claim 1, wherein the cementitious material in step (2) comprises cement and ground copper slag powder, the ground copper slag powder being 25-30% of the total amount of cementitious material.
5. The method for preparing the environment-friendly high-performance radiation-resistant shielding concrete according to claim 1, wherein the weight ratio of the surface-reinforced CRT glass powder fine aggregate to the river sand fine aggregate, the crushed stone coarse aggregate, the cementing material and the water in the step (2) is 4.31:6.74:2.86:1, the graphene accounts for 3% of the weight of the cementing material, the mass ratio of the surface-reinforced CRT glass powder fine aggregate to the river sand fine aggregate is 4:6, and the high-efficiency water reducing agent accounts for 0.12% of the weight of the cementing material.
6. The method for preparing environment-friendly high-performance radiation-proof shielding concrete according to claim 1, wherein the fresh radiation-proof concrete in the step (2) is prepared from the following components in parts by weight: 320-325 parts of cement, 135-140 parts of ground copper slag powder, 13.5-14.0 parts of graphene, 415-420 parts of river sand fine aggregate, 275-280 parts of reinforced waste CRT glass powder fine aggregate, 1085-1090 parts of crushed stone coarse aggregate and 160-165 parts of mixed water doped with a polycarboxylic acid high-efficiency water reducer.
7. The method for preparing an environmentally friendly, high performance radiation protective shielding concrete according to claim 1, wherein step (3) comprises the steps of: and (3) accelerating stirring of the freshly mixed concrete slurry, taking part of freshly mixed concrete, pouring the freshly mixed concrete into test molds respectively to prepare samples, covering the concrete test molds by wet gunny bags, placing the concrete test molds in a room with the temperature of 25 ℃ and the humidity of 55-65%, removing the concrete test molds after 24 hours, and transferring the concrete test specimens into a standard carbonization environment to be cured for a specified age.
8. The method of preparing an environmentally friendly, high performance radiation protective shielding concrete according to claim 7, wherein the test pattern comprises 100mm x 100 x mm x 100mm, 150mm x 150 x mm x 550mm, 100mm x 100mm x 300mm, phi 40mm x 80mm.
9. The method for preparing environment-friendly high-performance radiation-proof shielding concrete according to claim 7, wherein the standard carbonization maintenance environment is CO 2 The concentration is 2+/-0.5%, the temperature is 20+/-5% and the humidity is 70+/-5%.
10. The environment-friendly high-performance radiation-resistant shielding concrete prepared by the method of any one of claims 1-9.
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