CN115521121A - Corrosion-resistant cement mortar and preparation method thereof - Google Patents
Corrosion-resistant cement mortar and preparation method thereof Download PDFInfo
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- CN115521121A CN115521121A CN202211261575.XA CN202211261575A CN115521121A CN 115521121 A CN115521121 A CN 115521121A CN 202211261575 A CN202211261575 A CN 202211261575A CN 115521121 A CN115521121 A CN 115521121A
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- parts
- corrosion
- water
- cement mortar
- stirring
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- 238000005260 corrosion Methods 0.000 title claims abstract description 82
- 230000007797 corrosion Effects 0.000 title claims abstract description 81
- 239000011083 cement mortar Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000003607 modifier Substances 0.000 claims abstract description 49
- 239000004568 cement Substances 0.000 claims abstract description 30
- 239000003112 inhibitor Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000004576 sand Substances 0.000 claims abstract description 23
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 86
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 60
- 239000004570 mortar (masonry) Substances 0.000 claims description 48
- 239000000725 suspension Substances 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 235000021355 Stearic acid Nutrition 0.000 claims description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 17
- 239000008117 stearic acid Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000395 magnesium oxide Substances 0.000 claims description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000011398 Portland cement Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 2
- 239000011401 Portland-fly ash cement Substances 0.000 claims 1
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 abstract description 32
- 230000002209 hydrophobic effect Effects 0.000 abstract description 19
- 235000019359 magnesium stearate Nutrition 0.000 abstract description 16
- 239000000839 emulsion Substances 0.000 abstract description 15
- -1 2-mercapto-1-methylimidazole modified cobaltosic oxide Chemical class 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 45
- 239000004567 concrete Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006703 hydration reaction Methods 0.000 description 12
- 230000036571 hydration Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000004729 solvothermal method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 description 5
- 229910001653 ettringite Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000003487 anti-permeability effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VBQMPXNFLQSHMH-UHFFFAOYSA-N Arlatin Chemical compound C1CC(C)(O)C2(O)CC=C(C)C2C2OC(=O)C(C)C21 VBQMPXNFLQSHMH-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Images
Classifications
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- 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
- C04B28/04—Portland 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
- 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
- C04B22/085—Acids or salts thereof containing nitrogen in the anion, e.g. nitrites
-
- 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
- C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C04B24/085—Higher fatty acids
-
- 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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
-
- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses corrosion-resistant cement mortar and a preparation method thereof, wherein the corrosion-resistant cement mortar is prepared from the following raw materials in parts by weight: 20-50 parts of cement, 60-150 parts of sand, 3-6 parts of corrosion inhibitor, 1-3 parts of modifier and 8-20 parts of water. The corrosion-resistant cement mortar is prepared by combining calcium nitrate tetrahydrate, ferric nitrate nonahydrate, aluminum nitrate nonahydrate and polyvinylpyrrolidone, preparing a modifier by reacting hydrothermally prepared 2-mercapto-1-methylimidazole modified cobaltosic oxide and magnesium stearate emulsion, and mixing the corrosion inhibitor and the modifier with the cement mortar. Compared with the prior art, the corrosion-resistant cement mortar prepared by the invention has the advantages of high mechanical strength, good dry shrinkage deformation performance, strong hydrophobic performance, corrosion resistance and wide application range.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to corrosion-resistant cement mortar and a preparation method thereof.
Background
Concrete is an artificial material which cannot be replaced and widely applied in construction, and the key for supporting infrastructure is to improve the corrosion resistance of concrete in severe environment. However, the complex nature of the environment, particularly the high concentration of corrosive ions in extreme environments, greatly reduces the stability of the concrete in use, leading to deterioration of the concrete structure. In addition, the steel bars in the concrete are easy to generate electrochemical reaction, so that the concrete is peeled, longitudinal cracks are formed on the surface, and the bonding performance is degraded. In order to mitigate the permeability of corrosive ions, it is critical to develop a preservative that prevents the binding and transfer of corrosive ions in concrete. In the prior art, the following methods are mainly adopted, namely, a surface coating, a corrosion inhibitor, sacrificial anode protection, anti-cracking cementing material combination and the like, but the surface coating made of organic materials has strong toughness and excellent water resistance, but is easily influenced by poor abrasion and impact properties, and the adhesion and the flexibility of an inorganic coating are poor. On the other hand, the addition of the corrosion inhibitor relieves the corrosion of mortar, but the problem of difficult dispersion still exists, and the action time of the inorganic corrosion inhibitor is concentrated at the early stage of the service life of concrete.
Chinese invention patent CN108546024A discloses corrosion-resistant graphene cement mortar and a preparation method thereof. The method comprises the steps of loading graphene between layers of bentonite powder, mixing the graphene with cement, sand, coarse aggregate, water and a water reducing agent to prepare cement mortar, and spraying a cationic polyelectrolyte solution to prepare the corrosion-resistant graphene cement mortar. Compared with the traditional method, the prepared cement mortar has good dispersibility of the graphene in the cement mortar, good corrosion resistance and mechanical properties of cement mortar products and outstanding overall performance, and can be widely applied to the field of buildings. However, the method adopts graphene as the corrosion-resistant functional agent, and has the defects of high cost and poor concrete binding performance.
The publication number CN104496350A provides corrosion-resistant polymer modified cement mortar and a preparation method thereof: 1) Firstly, stirring and mixing cement, admixture and sand uniformly to obtain a mixture A; 2) Diluting the coupling agent with absolute ethyl alcohol, uniformly spraying the coupling agent on the surface of the mixture A, and then uniformly stirring and mixing to obtain a mixture B; 3) And mixing water, a water reducing agent, a polymer and an anti-aging agent to obtain a mixed solution, adding the mixed solution into the mixed solution B, uniformly stirring and mixing to obtain a mixed solution C, adding a defoaming agent into the mixed solution C, standing for 60-90 s, and uniformly stirring and mixing to obtain the polymer modified cement mortar. The invention selects the modified polymer with good performance, the coupling agent and the anti-aging agent, adopts a proper charging sequence and a stirring process, ensures that the polymer mortar really achieves long-acting corrosion resistance, has simple and easy operation preparation method, and is suitable for mass production. However, the polymer of the invention is at least one of ethylene-polyvinyl acetate or acrylic emulsion, and the prepared cement mortar has poor flexibility and dispersibility and low mechanical strength.
Therefore, the invention researches a preparation method of the cement mortar corrosion inhibitor. The corrosion inhibitor prepared by the method has good stability and excellent performance. By Fe 3+ Substituted Al 3+ The positive charge on the surface is increased, and the bonding between the double hydroxide radical layer and the metal ion layer is enhanced. The additive can effectively block the transfer of corrosive ions when added into cement mortar, and has good anti-corrosion effect.
Disclosure of Invention
In view of the defects of poor dispersibility and easy corrosion of cement mortar in the prior art, the invention aims to solve the technical problems that a modifier is prepared by reacting hydrothermally prepared 2-sulfydryl-1-methylimidazole modified cobaltosic oxide with magnesium stearate emulsion, a corrosion inhibitor is prepared by combining calcium nitrate tetrahydrate, ferric nitrate nonahydrate and aluminum nitrate nonahydrate with polyvinylpyrrolidone, and the corrosion-resistant cement mortar is provided by treating the cement mortar by adopting the modifier and the corrosion inhibitor.
The improvement of the water resistance and the impermeability of the cement mortar is an important way for improving the durability of the cement mortar. Currently, the most common methods are classified into surface modification and additive modification. The surface hydrophobic modification method is to perform hydrophobic modification on the surface after the concrete is cured so as to form a hydrophobic protective layer on the surface of the concrete, and is generally realized by surface coating or dipping. The methods of surface hydrophobic modification have a number of disadvantages. When the concrete is exposed to the external environment, the surface coating tends to age, the concrete is easy to crack, the surface hydrophobic layer is cracked and peeled off, and the waterproof and anti-permeability performance of the concrete is rapidly reduced. Additive modification may be a more effective way than surface modification. The modifying of the additive is to add the modifier in the stirring process of the concrete, and improve the waterproof and anti-permeability performance of the surface and the interior of the concrete. Therefore, compared with the surface hydrophobic modification method, the concrete prepared by the hydrophobic additive method has better performance and longer service life. The hydrophobicizers used at present are mainly liquid silanes and siloxanes, silane emulsions, hydrophobic stearic acid. The inventor carries out optimization adjustment on the added hydrophobic agent on the basis of modification of the additive, and finds that the introduction of silane or siloxane inhibits the hydration of cement to a certain extent. This is probably because the hydrophobic nature of the silane somewhat weakens the interaction forces between the aggregate and the hydration products at the interface. Stearic acid or stearic acid derivatives are difficult to be uniformly dispersed in a cement mortar system. Therefore, modifying the conventional hydrophobizing agent to reduce the influence of the conventional hydrophobizing agent on cement hydration and improve the dispersion of the hydrophobizing agent in mortar is an effective way to improve durability. Stearic acid is less costly and derivatives are easier to prepare than silanes and siloxanes. According to the invention, stearic acid, magnesium oxide and a surfactant are acted together to prepare a high-performance modifier which is added into the cement slurry.
However, the modifier of the invention is a nano magnesium stearate emulsion formed by heating reaction of stearic acid, magnesium oxide and a surfactant, has good dispersion property and low surface tension when being added into cement slurry, and has a promoting effect on initially hydrated ettringite, so that the cement mortar is integrally hydrophobic and the mechanical property of the cement mortar is improved. But after the modifier is added, the hydration speed of the cement is accelerated, the release of hydration heat is accelerated, and the self-contraction performance of the cement mortar is improved. In order to solve the problem, the invention discovers that the added structured cobaltosic oxide can be used as a template formed by early ettringite through a large number of experiments, delays the release of hydration heat, stabilizes the structure of a hydration product, and reduces the influence of a modifier on the self-shrinkage of cement mortar.
In order to achieve the purpose, the invention provides corrosion-resistant cement mortar which comprises the following raw materials: cement, sand, modifier and water.
Preferably, the corrosion-resistant cement mortar comprises the following raw materials in parts by weight: 20 to 50 portions of cement, 60 to 150 portions of sand, 1 to 3 portions of modifier and 8 to 20 portions of water.
Further preferably, the corrosion-resistant cement mortar is prepared from the following raw materials in parts by weight: 20 to 50 parts of cement, 60 to 150 parts of sand, 3 to 6 parts of corrosion inhibitor, 1 to 3 parts of modifier and 8 to 20 parts of water.
Preferably, the cement is one of ordinary portland cement, slag portland cement and fly ash portland cement.
The sand is common river sand with the grain diameter of 0.35-0.5 mm.
The preparation method of the cement mortar comprises the following steps: weighing raw materials according to a formula, putting cement, sand, a corrosion inhibitor, a modifier and water into a stirrer, stirring for 1-4 min at a stirring speed of 70-100 r/min, then filling into a mold, vibrating for 10-20 s while filling mortar, and scraping the surface of the mold by using a lime cutter after filling; and then placing the mould with the mortar in an environment with the temperature of 18-22 ℃ and the relative humidity of 85-92% for maintenance, demolding after 40-50 h, and maintaining until the curing time is 26-30 days to obtain the corrosion-resistant cement mortar.
The preparation method of the modifier comprises the following steps:
(1) Dispersing magnesium oxide in water to form a suspension;
(2) Heating and melting stearic acid, adding a nonionic surfactant and water, then adding ammonia water, and stirring to form a system I; and (3) dropwise adding the suspension obtained in the step (1) into the continuously stirred system I, continuing to react after dropwise adding, and adjusting the solid content after cooling to obtain the modifier.
Further, the preparation method of the modifier comprises the following steps of:
(1) Mixing 3-5 parts of magnesium oxide with 20-30 parts of water, treating for 20-60 min under the ultrasonic power of 50-100W, and then continuously stirring to form suspension;
(2) Heating and melting 20-50 parts of stearic acid at 70-90 ℃, adding 1-3 parts of nonionic surfactant and 100-150 parts of water, and stirring for 30-60 min; then adding 0.3-1 part of ammonia water, and continuously stirring and reacting for 30-60 min to form a body system I; dropwise adding the suspension obtained in the step (1) into the system I which is continuously stirred, and continuously stirring and reacting for 30-60 min after completely dropwise adding; naturally cooling to 20-30 ℃, and adjusting the solid content to 20-30% by using water to obtain the modifier.
More preferably, the preparation method of the modifier comprises the following steps:
(1) Mixing soluble metal cobalt salt with an organic solvent, stirring to form a solution, carrying out thermal reaction on the solvent, collecting insoluble substances, washing, drying, calcining, crushing and sieving to obtain cobaltosic oxide;
(2) Dispersing magnesium oxide in water to form a suspension;
(3) Heating and melting stearic acid, adding a nonionic surfactant and water, then adding ammonia water, and stirring to form a system I; and (3) dropwise adding the turbid liquid obtained in the step (2) into the continuously stirred system I, adding the cobaltosic oxide obtained in the step (1) after dropwise adding, continuing to react, cooling, and adjusting the solid content to obtain the modifier.
In some preferred embodiments, the preparation method of the modifier comprises the following steps in parts by weight:
(1) Mixing 0.5-1 part of cobalt nitrate hexahydrate, 20-30 parts of isopropanol and 5-10 parts of glycerol, and stirring for 30-60 min to form a solution; carrying out solvothermal reaction on the solution at 160-180 ℃ for 6-8 h, naturally cooling, collecting insoluble substances, washing, drying, calcining, crushing and sieving to obtain cobaltosic oxide;
(2) Mixing 3-5 parts of magnesium oxide with 20-30 parts of water, treating for 20-60 min under the ultrasonic power of 50-100W, and then continuously stirring to form suspension;
(3) Heating and melting 20-50 parts of stearic acid at 70-90 ℃, adding 1-3 parts of nonionic surfactant and 100-150 parts of water, and stirring for 30-60 min; then adding 0.3-1 part of ammonia water, and continuously stirring and reacting for 30-60 min to form a body system I; dropwise adding the suspension obtained in the step (2) into the continuously stirred system I, completely dropwise adding 1-5 parts of cobaltosic oxide prepared in the step (1), and continuously stirring for reaction for 30-60 min; naturally cooling to 20-30 ℃, and adjusting the solid content to 20-30% by using water to obtain the modifier.
Most preferably, the preparation method of the modifier comprises the following steps in parts by weight:
(1) Mixing 0.5-1 part of cobalt nitrate hexahydrate, 0.05-0.1 part of 2-mercapto-1-methylimidazole, 20-30 parts of isopropanol and 5-10 parts of glycerol, and stirring for 30-60 min to form a solution; carrying out solvothermal reaction on the solution at 160-180 ℃ for 6-8 h, naturally cooling, collecting insoluble substances, washing, drying, calcining, crushing and sieving to obtain cobaltosic oxide;
(2) Mixing 3-5 parts of magnesium oxide and 20-30 parts of water, treating for 20-60 min under the ultrasonic power of 50-100W, and then continuously stirring to form suspension;
(3) Heating and melting 20-50 parts of stearic acid at 70-90 ℃, adding 1-3 parts of nonionic surfactant and 100-150 parts of water, and stirring for 30-60 min; then adding 0.3-1 part of ammonia water, and continuously stirring and reacting for 30-60 min to form a body system I; dropwise adding the suspension obtained in the step (2) into the system I which is continuously stirred, completely dropwise adding 1-5 parts of cobaltosic oxide prepared in the step (1), and continuously stirring and reacting for 30-60 min; naturally cooling to 20-30 ℃, and adjusting the solid content to 20-30% by using water to obtain the modifier.
Preferably, the nonionic surfactant in the step (3) is at least one of fatty alcohol-polyoxyethylene ether O-20, fatty alcohol-polyoxyethylene ether O-25 and fatty alcohol-polyoxyethylene ether AEO-9.
The preparation method of the corrosion inhibitor comprises the following steps:
s1, adding calcium nitrate tetrahydrate, ferric nitrate nonahydrate and aluminum nitrate nonahydrate into water to prepare a mixed solution, dropwise adding the mixed solution into a sodium hydroxide aqueous solution, stirring to prepare a suspension, then placing the suspension in a nitrogen environment, stirring, collecting a precipitate, washing with water to be neutral, drying, grinding and sieving to obtain mixed fine powder;
and S2, dissolving polyvinylpyrrolidone in water for dispersion, then adding the mixed fine powder prepared in the step S1, and performing dispersion treatment to obtain the corrosion inhibitor.
Further preferably, the preparation method of the corrosion inhibitor comprises the following steps of:
s1, adding 8-12 parts of calcium nitrate tetrahydrate, 0.5-2 parts of ferric nitrate nonahydrate and 3-5 parts of aluminum nitrate nonahydrate into 80-120 parts of water to prepare a mixed solution, dropwise adding the mixed solution into 80-120 parts of 0.1-0.2 mol/L sodium hydroxide aqueous solution at a dropping speed of 3-6L/min, magnetically stirring for 10-30 min at a stirring speed of 200-400 r/min to prepare a suspension, then placing the suspension in a nitrogen environment, magnetically stirring for 20-30 h at 20-30 ℃ at a stirring speed of 500-800 r/min, collecting precipitates, washing the precipitate to be neutral, drying for 10-20 h at 70-100 ℃, grinding and sieving to obtain mixed fine powder;
s2, dissolving 15-30 parts of polyvinylpyrrolidone in 80-150 parts of water, performing ultrasonic dispersion for 3-10 min, adding the mixed fine powder prepared in the step S1, and continuing performing ultrasonic dispersion for 0.5-2 h to obtain the corrosion inhibitor.
Preferably, the sieving in the step S1 is performed by adopting a 400-600 mesh sieve.
The corrosion inhibitor can obviously improve the corrosion resistance of cement mortar, and the polyvinylpyrrolidone is a dispersible surfactant and can form a protective film on the surface of a metal compound, promote the uniform dispersion between the metal compound and cement, avoid particle agglomeration and improve the compactness and impedance of a sample. And the barrier effect on corrosive ions can be improved, the migration of the corrosive ions is reduced, and cement mortar prepared by adding the corrosion inhibitor has good corrosion resistance and better application prospect.
The invention has the beneficial effects that:
(1) Mixing magnesium oxide and stearic acid, adding a nonionic surfactant, preparing a magnesium stearate emulsion by using a simple chemical reaction, and taking the magnesium stearate emulsion as a modifier of cement mortar, thereby obviously improving the hydrophobic properties of the inner and outer surfaces of the mortar;
(2) The cobaltosic oxide is added, so that the hydrophobic property of the mortar is further improved, the mechanical strength, the water resistance and the chloride ion resistance of the mortar are improved, and the shrinkage property of the cement mortar is improved;
(3) The corrosion inhibitor prepared by compounding calcium nitrate tetrahydrate, ferric nitrate nonahydrate, aluminum nitrate nonahydrate and polyvinylpyrrolidone improves the barrier effect of cement mortar on corrosive ions, and the prepared cement mortar has good corrosion resistance.
Drawings
FIG. 1 is a scanning electron micrograph of tricobalt tetraoxide prepared in examples of the present invention and comparative examples; fig. 1A shows comparative example 2, fig. 1B shows example 2, and fig. 1C shows example 3.
Detailed Description
Introduction of some materials in the examples of the present invention:
cement, portland cement PO 42.5, available from new cement limited, north Hubei.
River sand, a common river sand belonging to grade i sand, was purchased from shijiazhuang zhou lin mineral products ltd.
Fatty alcohol-polyoxyethylene ether AEO-9, available from Shandong sanden New Material science and technology Co.
2-mercapto-1-methylimidazole, available from Shanghai Arlatin Biotechnology Ltd.
Calcium nitrate tetrahydrate, ferric nitrate nonahydrate and aluminum nitrate nonahydrate were all available from merck corporation.
Polyvinylpyrrolidone, available from Shanghai Allantin Biotechnology Ltd.
The preparation method of the corrosion-resistant cement mortar test piece comprises the following steps: putting the corrosion-resistant cement mortar components in the embodiment and the comparative example of the invention into a stirrer, stirring for 2min at a stirring speed of 80r/min, then filling the components into a mould, vibrating for 15s while filling the mortar, and scraping the surface of the mould by using a lime knife after filling; and then, placing the mould with the mortar in an environment with the temperature of 20 ℃ and the relative humidity of 90% for maintenance, demolding after 48 hours, and maintaining until the curing time is 28 days to obtain the corrosion-resistant cement mortar test piece.
The test piece of 40mm multiplied by 160mm is used for testing the strength, self-contraction and chemical corrosion resistance of the mortar; the test piece of 70.7mm multiplied by 70.7mm is used for testing the water absorption of the mortar; a cylindrical test piece having a diameter of 100mm and a height of 50mm was used for the chloride permeability test of the mortar.
Example 1
A corrosion-resistant cement mortar is composed of 20kg of cement, 60kg of river sand, 1kg of modifier and 8.2kg of water.
The preparation method of the modifier comprises the following steps:
(1) Mixing 3kg of magnesium oxide with 25kg of water, treating for 30min at an ultrasonic power of 50W and a frequency of 40kHz, and then stirring for 30min at a stirring speed of 350r/min to form a suspension;
(2) Heating 3.5kg of stearic acid for melting at 80 ℃, adding 1kg of fatty alcohol-polyoxyethylene ether AEO-9 and 100kg of water, and stirring for 30min at a stirring speed of 350 r/min; then adding 0.5kg of ammonia water, and continuously stirring and reacting for 3min to form a body system I; dropwise adding the suspension obtained in the step (1) into the continuously stirred system I at a dropwise adding rate of 0.5kg/min, and continuously stirring and reacting for 30min after completely dropwise adding; naturally cooling to 25 ℃, and adjusting the solid content to 25% by using water to obtain the modifier.
Example 2
A corrosion-resistant cement mortar is composed of 20kg of cement, 60kg of river sand, 1kg of modifier and 8.2kg of water.
The preparation method of the modifier comprises the following steps:
(1) Mixing 0.8kg of cobalt nitrate hexahydrate, 25kg of isopropanol and 5kg of glycerol, and stirring at the stirring speed of 450r/min for 30min to form a solution; transferring the solution to a reaction kettle, carrying out solvothermal reaction at 180 ℃ for 8h, naturally cooling to 25 ℃, collecting insoluble substances, washing with acetone and water for three times respectively, drying in a constant-temperature oven at 80 ℃ for 6h, transferring to a muffle furnace at 550 ℃ for calcining for 2h, naturally cooling to 25 ℃, crushing, and screening by a 325-mesh screen to obtain cobaltosic oxide;
(2) Mixing 3kg of magnesium oxide with 25kg of water, treating for 30min at an ultrasonic power of 50W and a frequency of 40kHz, and then stirring for 30min at a stirring speed of 350r/min to form a suspension;
(3) Heating and melting 3.5kg of stearic acid at the temperature of 80 ℃, adding 1kg of fatty alcohol-polyoxyethylene ether AEO-9 and 100kg of water, and stirring for 30min at the stirring speed of 350 r/min; then 0.5kg of ammonia water is added, and the mixture is continuously stirred and reacts for 3min to form a body system I; dropwise adding the suspension obtained in the step (2) into the continuously stirred system I at the dropwise adding speed of 0.5kg/min, after completely dropwise adding, adding 2kg of the cobaltosic oxide prepared in the step (1), and continuously stirring and reacting for 30min; naturally cooling to 25 ℃, and adjusting the solid content to 25% by using water to obtain the modifier.
Example 3
A corrosion-resistant cement mortar is composed of 20kg of cement, 60kg of river sand, 1kg of modifier and 8.2kg of water.
The preparation method of the modifier comprises the following steps:
(1) Mixing 0.8kg of cobalt nitrate hexahydrate, 0.05kg of 2-mercapto-1-methylimidazole, 25kg of isopropanol and 5kg of glycerol, and stirring at the stirring speed of 450r/min for 30min to form a solution; transferring the solution to a reaction kettle, carrying out solvothermal reaction for 8h at 180 ℃, naturally cooling to 25 ℃, collecting insoluble substances, washing with acetone and water for three times respectively, drying in a constant-temperature oven at 80 ℃ for 6h, transferring to a muffle furnace at 550 ℃ for calcining for 2h, naturally cooling to 25 ℃, crushing, and screening with a 325-mesh screen to obtain cobaltosic oxide;
(2) Mixing 3kg of magnesium oxide with 25kg of water, treating for 30min at an ultrasonic power of 50W and a frequency of 40kHz, and then stirring for 30min at a stirring speed of 350r/min to form a suspension;
(3) Heating and melting 3.5kg of stearic acid at the temperature of 80 ℃, adding 1kg of fatty alcohol-polyoxyethylene ether AEO-9 and 100kg of water, and stirring for 30min at the stirring speed of 350 r/min; then adding 0.5kg of ammonia water, and continuously stirring and reacting for 3min to form a body system I; dropwise adding the suspension obtained in the step (2) into the continuously stirred system I at the dropwise adding speed of 0.5kg/min, after completely dropwise adding, adding 2kg of the cobaltosic oxide prepared in the step (1), and continuously stirring and reacting for 30min; naturally cooling to 25 ℃, and adjusting the solid content to 25% by using water to obtain the modifier.
Example 4
The corrosion-resistant cement mortar consists of 20kg of cement, 60kg of river sand, 4kg of corrosion inhibitor, 1kg of modifier and 8.2kg of water.
The preparation method of the modifier comprises the following steps:
(1) Mixing 0.8kg of cobalt nitrate hexahydrate, 0.05kg of 2-mercapto-1-methylimidazole, 25kg of isopropanol and 5kg of glycerol, and stirring at the stirring speed of 450r/min for 30min to form a solution; transferring the solution to a reaction kettle, carrying out solvothermal reaction for 8h at 180 ℃, naturally cooling to 25 ℃, collecting insoluble substances, washing with acetone and water for three times respectively, drying in a constant-temperature oven at 80 ℃ for 6h, transferring to a muffle furnace at 550 ℃ for calcining for 2h, naturally cooling to 25 ℃, crushing, and screening with a 325-mesh screen to obtain cobaltosic oxide;
(2) Mixing 3kg of magnesium oxide with 25kg of water, treating for 30min at an ultrasonic power of 50W and a frequency of 40kHz, and then stirring for 30min at a stirring speed of 350r/min to form a suspension;
(3) Heating and melting 3.5kg of stearic acid at the temperature of 80 ℃, adding 1kg of fatty alcohol-polyoxyethylene ether AEO-9 and 100kg of water, and stirring for 30min at the stirring speed of 350 r/min; then adding 0.5kg of ammonia water, and continuously stirring and reacting for 3min to form a body system I; dropwise adding the suspension obtained in the step (2) into the continuously stirred system I at a dropwise adding rate of 0.5kg/min, adding 2kg of cobaltosic oxide prepared in the step (1) after completely dropwise adding, and continuously stirring and reacting for 30min; naturally cooling to 25 ℃, and adjusting the solid content to 25% by using water to obtain the modifier.
The preparation method of the corrosion inhibitor comprises the following steps:
s1, adding 1kg of calcium nitrate tetrahydrate, 0.1kg of ferric nitrate nonahydrate and 0.4kg of aluminum nitrate nonahydrate into 10kg of water to prepare a mixed solution, dropwise adding the mixed solution into 10 kgs of 0.12mol/L sodium hydroxide aqueous solution at the dropwise adding speed of 3-6L/min, magnetically stirring for 20min at the stirring speed of 300r/min to prepare a suspension, then placing the suspension in a nitrogen environment, magnetically stirring for 24h at the temperature of 25 ℃, collecting precipitates, washing the precipitates to be neutral, drying for 12h at the temperature of 80 ℃, and grinding through a 500-mesh sieve to obtain mixed fine powder;
s2, dissolving 2kg of polyvinylpyrrolidone in 10kg of water, performing ultrasonic dispersion for 5min, adding the mixed fine powder prepared in the step S1, and continuing performing ultrasonic dispersion for 1h to obtain the corrosion inhibitor.
Comparative example 1
A corrosion-resistant cement mortar is composed of 20kg of cement, 60kg of river sand, 1kg of modifier and 8.2kg of water.
The modifier is a suspension of 25wt% magnesium stearate.
Comparative example 2
A corrosion-resistant cement mortar is composed of 20kg of cement, 60kg of river sand, 1kg of modifier and 8.2kg of water.
The modifier comprises the following steps:
(1) Mixing 0.8kg of cobalt nitrate hexahydrate, 0.2kg of urea and 30kg of water, and stirring at the stirring speed of 450r/min for 30min to form a solution; transferring the solution to a reaction kettle, carrying out solvothermal reaction for 8h at 180 ℃, naturally cooling to 25 ℃, collecting insoluble substances, washing with acetone and water for three times respectively, drying in a constant-temperature oven at 80 ℃ for 6h, transferring to a muffle furnace at 550 ℃ for calcining for 2h, naturally cooling to 25 ℃, crushing, and screening with a 325-mesh screen to obtain cobaltosic oxide;
(2) Mixing 3kg of magnesium oxide with 25kg of water, treating for 30min at an ultrasonic power of 50W and a frequency of 40kHz, and then stirring for 30min at a stirring speed of 350r/min to form a suspension;
(3) Heating and melting 3.5kg of stearic acid at the temperature of 80 ℃, adding 1kg of fatty alcohol-polyoxyethylene ether AEO-9 and 100kg of water, and stirring for 30min at the stirring speed of 350 r/min; then adding 0.5kg of ammonia water, and continuously stirring and reacting for 3min to form a body system I; dropwise adding the suspension obtained in the step (2) into the continuously stirred system I at a dropwise adding rate of 0.5kg/min, adding 2kg of cobaltosic oxide prepared in the step (1) after completely dropwise adding, and continuously stirring and reacting for 30min; naturally cooling to 25 ℃, and adjusting the solid content to 25% by using water to obtain the modifier.
Test example 1
The compressive strength of cement mortar test pieces of 40mm x 160mm were tested by reference to the test method for cement mortar strength of standard GB/T17671-1999 (ISO method), and the results are shown in Table 1. The components of the conventional mortars in the table are substantially the same as in example 1, with the only difference that no modifier is added.
TABLE 1 Strength test results of Cement mortars
From the results in Table 1, it can be seen that comparative example 1, in which magnesium stearate suspension was added as an improver, rather decreased the compressive strength relative to the conventional mortar. This is probably due to the hydrophobic nature of magnesium stearate, which somewhat weakens the interaction of the aggregate with the cement in the interfacial transition zone. The compressive strength of example 1 with the addition of magnesium stearate composite emulsion is slightly higher than that of ordinary mortar, probably because early magnesium stearate composite emulsion can promote the forward progress of hydration reaction without consuming calcium hydroxide, thereby increasing cement hydration products and slightly improving the strength of cement mortar. In comparative example 2, example 2 and example 3, cobaltosic oxide is also added into the magnesium stearate composite emulsion, so that the compressive strength is further improved. The reason is probably that the cobaltosic oxide can be used as an initial template formed by ettringite to promote hydration products to form a more stable structure, and cobaltosic oxide particles with high mechanical properties can bear part of stress, so that the strength of the mortar test piece is improved. As shown in fig. 1, it can be seen that there is a significant difference in the structure of the cobaltosic oxide of comparative example 2, and example 3. Hydrothermally prepared cobaltosic oxide (fig. 1A, example 1) is in a lamellar aggregated structure; the cobaltosic oxide of example 2 (fig. 1B) appears spherical; example 3 (fig. 1C) is a structured multilayered sheet. Probably due to the structure of cobaltosic oxide, the cement mortar of example 3 has the best compressive strength.
Test example 2
The water contact angle of the test piece may reflect the hydrophilicity of the test piece. And wetting the surface of the object to be detected with water, wherein the contact angle is more than 90 degrees and is hydrophobic. The cement mortar test pieces of 40mm × 40mm × 160mm were cut, and the water contact angles of the inner and outer surfaces of the cement mortar were measured, with the results shown in table 2.
TABLE 2 Water contact Angle of the inner and outer surfaces of the test pieces
Experimental protocol | Inner surface water contact angle (°) | External surface water contact angle (°) |
Ordinary mortar | 26 | 35 |
Example 1 | 83 | 119 |
Example 2 | 93 | 128 |
Example 3 | 101 | 134 |
Example 4 | 98 | 130 |
Comparative example 1 | 61 | 113 |
Comparative example 2 | 88 | 123 |
As can be seen from the test results of Table 2, both the inner and outer surfaces of the cement mortar without the modifier are hydrophilic. The addition of magnesium stearate in comparative example 1 improves the hydrophilicity of the mortar and reverses the wetting of the outer surface. The hydrophilicity of the mortar test pieces of example 1 to which the magnesium stearate emulsion was added was further improved, but the interior of the mortar was still hydrophilic. The same is true for comparative example 2. The mortars of example 2 and example 3 were both hydrophobic on both the inner and outer surfaces. This may be related to the structure of the cobaltosic oxide. The mortar of comparative example 3 has the best hydrophobicity, which is probably because the addition of 2-mercapto-1-methylimidazole not only improves the structure of cobaltosic oxide, but also enhances the dispersibility thereof in an emulsion system, so that a hydrophobic membrane is more easily formed.
The water absorption of a mortar sample of 70.7mm × 70.7mm × 70.7mm was tested with reference to standard JC 474-2008 mortar and concrete waterproofing agent. Drying the standard mortar sample and the mortar sample to be tested in a constant temperature oven at 80 ℃ to constant weight, respectively weighing and recording the weight m t1 And m 1 (ii) a Then placing the mortar sample into a tank with two steel bars at the bottom, immersing the standard mortar sample and the mortar sample to be tested into water with the height of 35mm and the water surface constant, keeping the mortar sample at 20 ℃ and the relative humidity of 90% for 48 hours, taking out the mortar sample, wiping the water on the surface of the test piece, weighing and recording the weight m of the standard mortar sample and the mortar sample to be tested respectively t1 And m 2 (ii) a Calculated Water absorption = (m) 2 -m 1 )/(m t2 -m t1 ). The results are shown in Table 3.
TABLE 3 Water absorption results for the test pieces
Experimental protocol | Water absorption (%) |
Ordinary mortar | 4.5 |
Examples1 | 2.6 |
Example 2 | 2.1 |
Example 3 | 1.8 |
Example 4 | 1.9 |
Comparative example 1 | 4.3 |
Comparative example 2 | 2.4 |
As can be seen from the test results in the table above, the cement mortar test piece prepared in example 3 of the present invention has the lowest water absorption amount, because the inside and outside of the mortar are hydrophobic, water drops are repelled from the surface and are difficult to penetrate into pores, and the water absorption amount is significantly reduced; the cobaltosic oxide has a certain water retention effect, so that the free water content in the new mortar is reduced, micropores and capillary holes in the hydration and maintenance processes of the cement mortar are reduced, and the passing way of water in the mortar is reduced.
Test example 3
According to the standard of the test method of the long-term performance and the durability of the standard GB/T50082-2009 common concrete, the chloride ion penetration resistance of a cylindrical cement mortar test piece with the diameter of 100mm and the height of 50mm is tested by adopting a rapid chloride ion migration coefficient method. The results are shown in Table 4. The lower the penetration depth, the lower the permeability coefficient, the better the chloride ion resistance.
TABLE 4 results of chloride ion penetration resistance of cement mortar test pieces
From the results in Table 4, it can be seen that the mortar prepared in example 4 of the present invention has the best anti-permeability, probably because polyvinylpyrrolidone is a dispersible surfactant, and can form a protective film on the surface of the metal compound, promote uniform dispersion between the metal compound and the cement, prevent particle agglomeration, and improve the compactness and resistance of the sample. But also improves the barrier effect to the corrosive ions, reduces the migration of the corrosive ions, reduces the diffusion channels of the chloride ions and obviously reduces the permeability coefficient of the chloride ions.
Test example 4
The self-contraction performance of the mortar test piece is tested according to the standard JGJ/T70-2009 building mortar basic performance test method. The results are shown in Table 5.
TABLE 5 self-shrinkage results for cement mortars
Experimental protocol | Self-contraction (mu epsilon) |
Ordinary mortar | -536 |
Example 1 | -628 |
Example 2 | -486 |
Example 3 | -432 |
Example 4 | -441 |
Comparative example 2 | -601 |
From the test results in the table above, it can be seen that the self-shrinkage rate of the test piece prepared by adding the magnesium stearate emulsion in example 1 is increased, which is probably because the hydrophobicity of the mortar test piece is enhanced, and the magnesium stearate promotes the hydration reaction, and consumes water, so that the self-drying effect inside the mortar is more obvious. Comparative example 2 also added hydrothermally prepared cobaltosic oxide, the self-shrinking property was improved, probably because the cobaltosic oxide acts as an ettringite template to refine the pore structure. Example 3, which incorporates the 2-mercapto-1-methylimidazole modified cobaltosic oxide and magnesium stearate emulsion, has the best self-shrinking properties, probably because of the good dispersibility, overall mortar hydrophobicity, refined pore structure, enhanced capillary pressure and internal stress, thus significantly improving the self-shrinking properties of the mortar.
Test example 5
Chemical resistance test
The test refers to the test method of master paper (study on the properties of epoxy resin emulsion modified cement mortar, author: xu Kuisheng, university of Chongqing traffic, 2012), the cement mortar test piece which reaches curing for 28 days is put into an oven at 80 ℃ to be dried for two hours. Three kinds of etching solutions were prepared, which were 10wt% sodium sulfate aqueous solution, 10wt% sodium hydroxide aqueous solution, and 5wt% sulfuric acid aqueous solution, respectively. The test pieces of the embodiment 3 and the embodiment 4 are respectively put into the three solutions and water, the temperature is 15-35 ℃ at room temperature, and the humidity is 50-85%. After soaking for 6 months, taking out and carrying out a bending test.
The mass loss rate calculation formula is as follows:
Δm=(m 0 -m 1 )/m 0
Δ m is mass loss rate%;
m 0 the oven-dried mass, g, of the test piece not subjected to immersion;
m 1 g, drying the test piece after soaking for 6 months;
using a coefficient of fracture resistance K p Evaluation of Corrosion resistance, K p The calculation formula is the ratio of the flexural strength of the series of test pieces after erosion to the flexural strength of the series of test pieces cured in water in the same age period as follows:
K p =R p /R 0
K p is the fracture resistance and corrosion resistance coefficient;
R p the flexural strength of the series of test pieces after corrosion;
R 0 the flexural strength of the series of test pieces was cured in water.
Examples 3 and 4 three samples were prepared for each example and the results were averaged and are shown in table 6.
TABLE 6 chemical resistance test results
Experimental protocol | Fracture and corrosion resistance coefficient | Mass loss rate/%) |
Example 3 | 0.81 | 2.85 |
Example 4 | 0.96 | 2.04 |
From the test results of table 6, it can be seen that the chemical corrosion resistance of example 4 is the best, probably because polyvinylpyrrolidone forms an organic passivation film on the surface of the metal compound, the compactness and the impedance of the metal compound are improved, the uniform dispersion of the metal compound in the slurry is promoted, the particle agglomeration is avoided, and the transport channel of corrosive ions is blocked, so that example 4 with the addition of the corrosion inhibitor has excellent corrosion resistance.
Claims (10)
1. The corrosion-resistant cement mortar is characterized by comprising the following raw materials: cement, sand, corrosion inhibitor, modifier and water.
2. The corrosion-resistant cement mortar of claim 1, which is prepared from the following raw materials in parts by weight: 20-50 parts of cement, 60-150 parts of sand, 3-6 parts of corrosion inhibitor, 1-3 parts of modifier and 8-20 parts of water.
3. The corrosion-resistant cement mortar of claim 1 or 2, wherein said cement is one of ordinary portland cement, portland slag cement, and portland fly ash cement.
4. The corrosion-resistant cement mortar of claim 1 or 2, wherein the sand is general river sand having a particle size of 0.35 to 0.5mm.
5. The corrosion-resistant cement mortar of claim 1 or 2, wherein said corrosion inhibitor is prepared by a method comprising the steps of:
s1, adding calcium nitrate tetrahydrate, ferric nitrate nonahydrate and aluminum nitrate nonahydrate into water to prepare a mixed solution, dropwise adding the mixed solution into a sodium hydroxide aqueous solution, stirring to prepare a suspension, then placing the suspension in a nitrogen environment, stirring, collecting a precipitate, washing with water to be neutral, drying, grinding and sieving to obtain mixed fine powder;
and S2, dissolving polyvinylpyrrolidone in water for dispersion, then adding the mixed fine powder prepared in the step S1, and performing dispersion treatment to obtain the corrosion inhibitor.
6. The corrosion-resistant cement mortar of claim 5, wherein the preparation method of the corrosion inhibitor comprises the following steps, the parts are all parts by weight:
s1, adding 8-12 parts of calcium nitrate tetrahydrate, 0.5-2 parts of ferric nitrate nonahydrate and 3-5 parts of aluminum nitrate nonahydrate into 80-120 parts of water to prepare a mixed solution, dropwise adding the mixed solution into 80-120 parts of 0.1-0.2 mol/L sodium hydroxide aqueous solution at a dropping speed of 3-6L/min, magnetically stirring for 10-30 min at a stirring speed of 200-400 r/min to prepare a suspension, then placing the suspension in a nitrogen environment, magnetically stirring for 20-30 h at 20-30 ℃ at a stirring speed of 500-800 r/min, collecting precipitates, washing with water to be neutral, drying for 10-20 h at 70-100 ℃, grinding and sieving to obtain mixed fine powder;
s2, dissolving 15-30 parts of polyvinylpyrrolidone in 80-150 parts of water, performing ultrasonic dispersion for 3-10 min, adding the mixed fine powder prepared in the step S1, and continuing performing ultrasonic dispersion for 0.5-2 h to obtain the corrosion inhibitor.
7. The corrosion-resistant cement mortar of claim 6, wherein the sieving in step S1 is performed by using a 400-600 mesh sieve.
8. The corrosion-resistant cement mortar of claim 1 or 2, wherein the preparation method of the modifier comprises the following steps, the parts are all parts by weight:
(1) Mixing 0.5-1 part of cobalt nitrate hexahydrate, 20-30 parts of isopropanol and 5-10 parts of glycerol, and stirring for 30-60 min to form a solution; carrying out thermal reaction on the solution at 160-180 ℃ for 6-8 h, naturally cooling, collecting insoluble substances, washing, drying, calcining, crushing and sieving to obtain cobaltosic oxide;
(2) Mixing 3-5 parts of magnesium oxide and 20-30 parts of water, treating for 20-60 min under the ultrasonic power of 50-100W, and then continuously stirring to form suspension;
(3) Heating and melting 20-50 parts of stearic acid at 70-90 ℃, adding 1-3 parts of nonionic surfactant and 100-150 parts of water, and stirring for 30-60 min; then adding 0.3-1 part of ammonia water, and continuously stirring and reacting for 30-60 min to form a body system I; dropwise adding the suspension obtained in the step (2) into the continuously stirred system I, completely dropwise adding 1-5 parts of cobaltosic oxide prepared in the step (1), and continuously stirring for reaction for 30-60 min; naturally cooling to 20-30 ℃, and adjusting the solid content to 20-30% by using water to obtain the modifier.
9. The corrosion-resistant cement mortar of claim 8, wherein said nonionic surfactant is at least one of fatty alcohol-polyoxyethylene ether O-20, fatty alcohol-polyoxyethylene ether O-25, fatty alcohol-polyoxyethylene ether AEO-9.
10. The preparation method of the corrosion-resistant cement mortar is characterized by comprising the following steps: putting raw materials of cement, sand, a corrosion inhibitor, a modifier and water in parts by weight into a stirrer, stirring for 1-4 min at a stirring speed of 70-100 r/min, then filling into a mold, vibrating for 10-20 s while filling mortar, and scraping the surface of the mold by using a lime cutter after filling; and then placing the mould with the mortar in an environment with the temperature of 18-22 ℃ and the relative humidity of 85-92% for maintenance, demolding after 40-50 h, and maintaining until the curing time is 26-30 days to obtain the corrosion-resistant cement mortar.
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