CN116835905A - Radiation-proof concrete additive and preparation method thereof - Google Patents
Radiation-proof concrete additive and preparation method thereof Download PDFInfo
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- CN116835905A CN116835905A CN202310805586.8A CN202310805586A CN116835905A CN 116835905 A CN116835905 A CN 116835905A CN 202310805586 A CN202310805586 A CN 202310805586A CN 116835905 A CN116835905 A CN 116835905A
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- 239000004567 concrete Substances 0.000 title claims abstract description 73
- 239000000654 additive Substances 0.000 title claims abstract description 25
- 230000000996 additive effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000005855 radiation Effects 0.000 claims abstract description 42
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000002562 thickening agent Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012452 mother liquor Substances 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 12
- 239000004814 polyurethane Substances 0.000 claims abstract description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000011814 protection agent Substances 0.000 claims abstract description 4
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- 239000000701 coagulant Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001488 sodium phosphate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 5
- 235000019800 disodium phosphate Nutrition 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- -1 alkyl phosphate Chemical compound 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000012986 chain transfer agent Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- CDVLCTOFEIEUDH-UHFFFAOYSA-K tetrasodium;phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O CDVLCTOFEIEUDH-UHFFFAOYSA-K 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims 1
- 229940072056 alginate Drugs 0.000 claims 1
- 235000010443 alginic acid Nutrition 0.000 claims 1
- 229920000615 alginic acid Polymers 0.000 claims 1
- 238000001935 peptisation Methods 0.000 claims 1
- 239000000718 radiation-protective agent Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 241001474374 Blennius Species 0.000 abstract description 10
- 238000005204 segregation Methods 0.000 abstract description 4
- 230000000740 bleeding effect Effects 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 239000010936 titanium Substances 0.000 description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 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
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 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
- 230000003471 anti-radiation Effects 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 230000007614 genetic variation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 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
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- 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
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/282—Polyurethanes; Polyisocyanates
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/38—Polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a radiation-proof concrete additive and a preparation method thereof, wherein the radiation-proof concrete additive is prepared from raw material bags in parts by weightComprises 20.0 to 40.0 parts of water-reducing mother liquor, 0.06 to 0.15 part of air entraining agent, 0.02 to 0.05 part of defoaming agent, 0.5 to 0.8 part of coagulant, 0.2 to 0.4 part of water-retaining thickener, and 0.5 to 1.0 part of radiation protection agent and water. According to the invention, the water retention thickener polyurethane associative thickener, the modified betaine and the seaweed gel are introduced into the radiation-proof concrete additive, so that the bleeding and segregation resistance of the concrete are improved, and the strength of the concrete is improved. The invention adds nano TiO 2 The sol and the nano-scale barium sulfate improve the radiation protection capability of the concrete. In the water-reducing mother liquor synthesis, ammonium acrylate is added to increase the dispersion performance of the solution, so that the titanium dioxide sol can be more uniformly dispersed in the whole additive and concrete besides enhancing the flow performance of the concrete.
Description
Technical Field
The invention relates to the technical field of concrete additives, in particular to an anti-radiation concrete additive and a preparation method thereof.
Background
Radiation refers to the transmission of energy in the form of electromagnetic waves or the movement of sub-atomic particles such as alpha, beta, gamma and neutron particles, the radiation energy being emitted straight away from the source in all directions. The penetration of alpha rays and beta rays is weak, and the alpha rays and the beta rays can be eliminated after being blocked by a common wall body, but the penetration of gamma rays and neutron rays is strong, the destructive power is high, and the symptoms such as cancer, leukemia, malignant tumor, infertility and the like are more easily induced after the human body is irradiated by the gamma rays and the neutron rays, and genetic teratogenesis is also possible. The plants may cause genetic variation and harm plant growth after being irradiated by gamma rays and neutron rays.
In places where radiation source buildings are built in scientific research institutions, hospitals and the like, the building construction is generally carried out by using radiation-proof materials, so that the radiation source is prevented from radiating outwards to cause harm to human bodies or animals and plants. Radiation-proof concrete is generally used for constructing radiation source buildings, and the radiation-proof concrete mainly prevents alpha, beta, gamma and neutron rays from penetrating through walls so as to cause injury to human bodies.
At present, the radiation protection concrete prepared at home and abroad mainly improves the radiation protection performance of the concrete by adding heavy metal element admixture, and in actual production, ores containing heavy metal elements such as serpentine, barite, limonite and the like are also used for improving the radiation protection capability of the concrete. Because gamma rays and neutron rays have strong penetrating power, the wall is generally required to be thickened, and the gamma rays and the neutron rays are prevented from penetrating through the wall.
In the use process of the radiation-proof concrete, the thickness of the wall body is generally required to be increased to slow down the speed of radiation rays, finally rays are blocked and absorbed, the radiation-proof performance is improved, the building cost is increased due to the increase of the thickness of the wall body, and meanwhile, the tensile property of the wall body is also influenced.
Disclosure of Invention
Based on the above, it is necessary to provide a radiation-proof concrete additive and a preparation method thereof, so as to solve the problems of high cost and poor radiation-proof effect of the radiation-proof concrete.
In order to achieve the above object, the present invention provides a technical solution:
the radiation-proof concrete additive comprises the following raw materials in parts by weight:
specifically, the air entraining agent comprises sodium dodecyl benzene sulfonate; the defoamer comprises polyether modified silicone oil.
Preferably, the radiation protection agent comprises nano TiO 2 At least one of sol and nano-sized barium sulfate.
The unique structure of the nano titanium dioxide particles causes the surface to generate surface effect, volume effect, quantum size effect and the like, so that the ultraviolet radiation resistance and the light radiation resistance of the nano titanium dioxide are greatly improved compared with those of the micro titanium dioxide, the covering capability of the nano titanium dioxide particles are also greatly improved, and the nano titanium dioxide particles can effectively defend the damage of gamma rays and beta rays in electromagnetic radiation, light radiation, heat radiation and nuclear radiation.
The nano-scale barium sulfate has good X-ray radiation resistance and strong defending ability against visible light or invisible light such as ultraviolet light, infrared light and the like with poorer X-ray penetrability due to the nano-structure property.
Preferably, nano TiO 2 The sol preparation steps are as follows:
mixing tetrabutyl titanate and an alcohol solution to obtain a tetrabutyl titanate mixed solution;
dropwise adding diluted hydrochloric acid to adjust the mixed solution of the tetrabutyl titanate to be acidic under magnetic stirring, slowly adding an ethanol solution into the mixed solution of the tetrabutyl titanate, and obtaining a pale yellow solution after the completion of the dropwise addition;
specifically, the alcohol solution comprises absolute ethanol and acetylacetone.
The hydrolysis reaction of tetrabutyl titanate in an ethanol medium is carried out stepwise under an acidic condition, wherein the total hydrolysis reaction is expressed as the following formula, and the hydrolysis product is titanium-containing ion sol, and the specific reaction formula is as follows:
Ti(O-C 4 H 9 ) 4 +4H 2 O→Ti(OH) 4 +4C 4 H 9 OH；
transferring the pale yellow solution into a three-neck flask, stirring in a water bath at 40 ℃ for 1 hour to obtain white sol, allowing titanium ions in the titanium ion-containing solution to interact with hydroxyl ions to form complex water and Ti-O-Ti three-dimensional network groups, naturally cooling, and performing ultrasonic dispergation to obtain stable TiO 2 Sol-gel
Ti(OH) 4 +Ti(O-C 4 H 9 ) 4 ＝2TiO 2 +4C 4 H 9 OH；
Ti(OH) 4 +Ti(OH) 4 ＝2TiO 2 (Sol) +4H 2 O。
Naturally cooling, and then adopting ultrasonic de-colloid to prepare transparent TiO 2 And (3) sol.
Preferably, the water-reducing mother liquor comprises the following preparation raw materials in parts by weight:
specifically, the mass concentration of the ferrous sulfate solution was 1%.
Preferably, the unsaturated acid monomer includes at least one of acrylic acid and methacrylic acid, which are available from satellite chemical Co., ltd.
Preferably, the preparation steps of the water-reducing mother solution are as follows:
the initial dripping temperature of the reaction is 10-15 ℃, and the polyethylene glycol macromonomer, the acrylamide and the oxidant are mixed to obtain a first mixed solution;
dropwise adding the solution A and the solution B into the first mixed solution, and carrying out heat preservation reaction for 1-3 h after the dropwise adding is finished to obtain a second mixed solution; the solution A comprises unsaturated acid monomer and water, and the solution B comprises reducing agent, chain transfer agent and water;
the time for dripping the solution A and the solution B is 30-50 min.
And regulating the pH value of the second mixed solution to 5-6 to obtain the water-reducing mother solution.
The structural formula of the water-reducing mother liquor is as follows:
wherein the ratio of a to b is 1: (3-5), n is an integer of 68-113.
Preferably, the oxidizing agent includes at least one of hydrogen peroxide and ammonium persulfate.
The reducing agent comprises one of ascorbic acid and ascorbic acid, and is available from Guangdong Europe and Style biotechnology Co., guangdong;
the chain transfer agent comprises at least one of sodium hypophosphite, thioglycollic acid, mercaptopropionic acid and mercaptoethanol, and is derived from Nanjing chess as a novel material company;
the ferrous sulfate solution and the acrylamide are both analytically pure, available from the company of the sciences, inc.
Preferably, the set-adjusting agent includes at least one of disodium phosphate, trisodium phosphate, tetrasodium phosphate, disodium hydrogen phosphate, sodium pyrophosphate, and alkyl phosphate.
The setting agent slows down the setting time of the concrete and enhances the construction performance of the concrete after the time.
Preferably, the water-retaining thickeners include polyurethane associative thickeners, modified betaines, and seaweed gums. The polyurethane associative thickener has the following structure:
in the above, R 1 Is a hydrophobic end group, R is alkane, m is an integer of 10-40, and n is an integer of 2-10.
The modified betaine is prepared from coconut oil serving as a raw material by condensation with N, N dimethyl propylene diamine to generate PKO and quaternization with sodium chloroacetate.
The polyurethane associative thickener and the modified betaine act together to enhance the viscosity and rheological property of water in the concrete, reduce the bleeding segregation and other states of the concrete, and the seaweed gel is dispersed and filled in a concrete system to form a reticular structure, so that the cohesiveness of the concrete is enhanced, the cavity gap in the concrete is reduced, and the strength of the concrete is enhanced.
The invention also provides a preparation method of the radiation-proof concrete additive, which comprises the following steps:
and stirring and mixing the water-reducing mother liquor and water, adding the air entraining agent, the defoaming agent, the coagulant and the water-retaining thickener while stirring, and finally adding the radiation protection agent to obtain the radiation protection concrete additive.
The invention has the beneficial effects that:
according to the invention, the water retention thickener polyurethane associative thickener, the modified betaine and the seaweed gel are introduced into the radiation-proof concrete additive, so that the bleeding and segregation resistance of the concrete are improved, and the strength of the concrete is improved.
The invention adds nano TiO 2 The sol and the nano-scale barium sulfate improve the radiation protection capability of the concrete.
In the water-reducing mother liquor synthesis, ammonium acrylate is added to increase the dispersion performance of the solution, so that the titanium dioxide sol can be more uniformly dispersed in the whole additive and concrete besides enhancing the flow performance of the concrete.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the examples, the test methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are commercially available.
Example 1
200kg of the water-reducing mother solution is put into a stirred tank, 1600kg of water is then put into the stirred tank, 0.6kg of air entraining agent sodium dodecyl benzene sulfonate, 0.2kg of defoamer polyether modified silicone oil, 5kg of disodium phosphate, 0.8kg of polyurethane association thickener, 0.8kg of modified betaine and 0.4kg of seaweed gel are put into the stirred tank, 4.5kg of nano titanium dioxide sol is put into the stirred tank, and finally 0.5kg of nano barium sulfate powder is put into the stirred tank for two hours before the additive test, and the mixture is stirred to form suspension, so that the radiation-proof concrete additive is obtained.
Example 2
200kg of the water-reducing mother solution is put into a stirred tank, 1600kg of water is then put into the stirred tank, 0.8kg of air entraining agent sodium dodecyl benzene sulfonate, 0.3kg of defoamer polyether modified silicone oil, 5kg of disodium phosphate, 1.0kg of polyurethane association thickener, 1.0kg of modified betaine and 0.5kg of seaweed gel are put into the stirred tank, 6.0kg of nano titanium dioxide sol is put into the stirred tank, and finally 0.5kg of nano barium sulfate powder is put into the stirred tank for two hours before the construction of the additive, and the mixture is stirred to form suspension, so that the radiation-proof concrete additive is obtained.
Example 3
200Kg of the water-reducing mother liquor is put into a stirred tank, 1600Kg of water is then put into the stirred tank, 0.8Kg of air entraining agent sodium dodecyl benzene sulfonate, 0.3Kg of defoamer polyether modified silicone oil, 5Kg of disodium phosphate, 1.0Kg of polyurethane association thickener, 1.0Kg of modified betaine and 0.5Kg of seaweed gel are put into the stirred tank, 8.0Kg of nano titanium dioxide sol is put into the stirred tank, and finally 0.5Kg of nano barium sulfate powder is put into the stirred tank for two hours before the construction of the additive, and the mixture is stirred to form suspension, so that the radiation-proof concrete additive is obtained.
Comparative example 1
Comparative example 1 was different from example 1 in that the admixture component contained no seaweed gel, and the other steps were the same as in example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that the admixture component does not contain a polyurethane associative thickener and a modified betaine, and the other steps are the same as in example 1.
Comparative example 3
Comparative example 3 is different from example 1 in that the additive component does not contain a nano-sized titania sol, and the other steps are the same as in example 1.
Comparative example 4
Comparative example 4 differs from example 1 in that the additive component does not contain nano-sized barium sulfate, and the other steps are the same as example 1.
Wherein, the preparation steps of the water-reducing mother liquor used in the examples and the comparative examples are as follows:
the method comprises the steps of (1) mixing 250 parts of polyethylene glycol macromonomer, 8 parts of acrylamide and 1 part of hydrogen peroxide to obtain a first mixed solution, wherein the initial dropwise adding temperature of the reaction is 15 ℃;
dropwise adding the solution A and the solution B into the first mixed solution, and carrying out heat preservation reaction for 1-3 h after the dropwise adding is finished to obtain a second mixed solution; the solution A comprises 30 parts of acrylic acid and water, and the solution B comprises 0.3 part of ascorbic acid, 1 part of thioglycollic acid and water;
the time for dropping the solution A and the solution B is 50min.
And regulating the pH value of the second mixed solution to 5-6 to obtain the water-reducing mother solution.
Nano TiO used in examples and comparative examples 2 The sol preparation steps are as follows:
mixing 100ml of tetrabutyl titanate with 350ml of absolute ethyl alcohol and 40ml of acetylacetone to obtain a tetrabutyl titanate mixed solution;
mixing 300 absolute ethyl alcohol and 100ml distilled water to prepare a dripping liquid;
and (3) under magnetic stirring, dropwise adding diluted hydrochloric acid to adjust the pH value of the mixed solution of the tetrabutyl titanate to be 2.5, slowly dropwise adding a dropwise adding liquid to the mixed solution of the tetrabutyl titanate, and obtaining a pale yellow solution after the dropwise adding is finished.
Transferring the solution into a three-neck flask, stirring in a water bath at 40 ℃ for 1 hour to obtain white sol, naturally cooling, and performing ultrasonic dispergation to obtain transparent nano TiO 2 And (3) sol.
The radiation-proof concrete admixture prepared in examples 1 to 3 and comparative examples 1 to 4 was applied to concrete, and concrete slump and expansion were tested according to the specification of GB/T50080. The concrete was tested for protection against radiation according to GB 18871. And (3) carrying out mechanical property test on the concrete according to GB 50080-2002. Gamma rays are measured by a nuclear radiation detector, and neutron rays are measured by a neutron source. Wherein, concrete is prepared according to the following table 1.
TABLE 1 concrete mix/m 3
| Intensity level | Cement/kg | Machine-made sand/kg | Crushed stone (10-20 mm)/kg | Water/kg |
| C30 | 380 | 980 | 1080 | 165 |
Table 2 shows the linear attenuation coefficients (cm) of the radiation protective concretes of examples 1 to 3 and comparative examples 1 to 4 -1 ) And (5) testing results.
TABLE 2 Linear attenuation coefficient (cm) of radiation protection concrete -1 )
As can be seen from the data in table 2, the linear attenuation coefficient of the radiation-proof concrete of example 1 for gamma rays and neutrons is significantly higher than that of comparative examples 1 to 2, and the linear attenuation coefficient of the radiation-proof concrete of examples 2 to 3 for gamma rays and neutrons is significantly higher than that of comparative examples 1 to 4; this shows that the radiation protection performance of the concrete is greatly improved by adding the novel radiation protection additive.
Table 3 shows the results of the workability test of the radiation protection concretes of examples 1 to 3 and comparative examples 1 to 4
TABLE 3 workability of radiation protection concrete
It can be seen from Table 3 that the concrete strength of the examples is significantly higher than that of the comparative examples.
As can be seen from the data of table 2 of example 1 and comparative example 1, without adding the nano-scale titania sol, the radiation protection performance of the concrete is reduced, which indicates that the nano-scale titania sol has a radiation protection effect.
As can be seen from the data of table 2 of example 1 and comparative example 2, without adding nano-sized barium sulfate, the radiation protection performance of the concrete is reduced, which indicates that the nano-sized barium sulfate has the radiation protection effect.
As can be seen from the data of table 3 of example 1 and comparative example 3, the concrete strength is reduced without adding seaweed gel, which indicates that the seaweed gel can effectively enhance the concrete strength.
As can be seen from the data in table 3 of example 1 and comparative example 4, the slump of concrete is obviously reduced without adding polyurethane associative thickener and modified betaine, which indicates that the polyurethane associative thickener and the modified betaine can effectively enhance the rheological property of concrete and improve the segregation state of concrete.
It should be noted that the specific parameters or some reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.
Claims (10)
1. The radiation-proof concrete additive is characterized by comprising the following raw materials in parts by weight:
2. the radiation protective concrete admixture of claim 1, wherein the radiation protective agent comprises nano TiO 2 At least one of sol and nano-sized barium sulfate.
3. The radiation protection concrete admixture according to claim 2, wherein nano TiO 2 The sol preparation steps are as follows:
mixing tetrabutyl titanate and an alcohol solution to obtain a tetrabutyl titanate mixed solution; dropwise adding diluted hydrochloric acid to adjust the mixed solution of the tetrabutyl titanate to be acidic under magnetic stirring, slowly adding an ethanol solution into the mixed solution of the tetrabutyl titanate, and obtaining a pale yellow solution after the completion of the dropwise addition;
transferring the pale yellow solution into a three-neck flask, stirring in a water bath at 40 ℃ for 1 hour to obtain white sol, naturally cooling, and performing ultrasonic peptization to obtain nano TiO 2 And (3) sol.
4. The radiation-proof concrete admixture according to claim 1, wherein the water-reducing mother liquor comprises the following raw materials in parts by weight:
5. the radiation protective concrete admixture of claim 4 wherein said unsaturated acid monomer comprises at least one of acrylic acid and methacrylic acid.
6. The radiation protection concrete admixture of claim 5, wherein said water-reducing mother liquor is prepared by the steps of:
mixing the polyethylene glycol macromonomer, the acrylamide and the oxidant to obtain a first mixed solution;
dropwise adding the solution A and the solution B into the first mixed solution, and carrying out heat preservation reaction for 1-3 h after the dropwise adding is finished to obtain a second mixed solution; the solution A comprises unsaturated acid monomer and water, and the solution B comprises reducing agent, chain transfer agent and water;
regulating the pH value of the second mixed solution to 5-6 to obtain the water-reducing mother solution;
the structural formula of the water-reducing mother liquor is as follows:
wherein the ratio of a to b is 1: (3-5), n is an integer of 68-113.
7. The radiation protective concrete admixture of claim 4 wherein said oxidizer comprises at least one of hydrogen peroxide and ammonium persulfate.
8. The radiation protective concrete admixture of claim 1, wherein said set control agent comprises at least one of disodium phosphate, trisodium phosphate, tetrasodium phosphate, disodium hydrogen phosphate, sodium pyrophosphate, and alkyl phosphate.
9. The radiation protective concrete admixture of claim 1 wherein the water retention thickener comprises a polyurethane associative thickener, a modified betaine, and an alginate gel.
10. A method for preparing the radiation-proof concrete admixture as claimed in any one of claims 1 to 9, comprising the steps of:
and stirring and mixing the water-reducing mother liquor and water, adding the air entraining agent, the defoaming agent, the coagulant and the water-retaining thickener while stirring, and finally adding the radiation protection agent to obtain the radiation protection concrete additive.
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