CN114656177A - Silicate cement with chlorine ion permeation resistance and preparation method thereof - Google Patents
Silicate cement with chlorine ion permeation resistance and preparation method thereof Download PDFInfo
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- CN114656177A CN114656177A CN202210506985.XA CN202210506985A CN114656177A CN 114656177 A CN114656177 A CN 114656177A CN 202210506985 A CN202210506985 A CN 202210506985A CN 114656177 A CN114656177 A CN 114656177A
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- portland cement
- graphene oxide
- chloride ion
- water
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003469 silicate cement Substances 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011398 Portland cement Substances 0.000 claims abstract description 45
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 10
- 239000010440 gypsum Substances 0.000 claims abstract description 9
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 9
- 239000010881 fly ash Substances 0.000 claims abstract description 8
- 235000019738 Limestone Nutrition 0.000 claims abstract description 7
- 239000000440 bentonite Substances 0.000 claims abstract description 7
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000006028 limestone Substances 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 121
- 229910021389 graphene Inorganic materials 0.000 claims description 94
- 239000000243 solution Substances 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000725 suspension Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 36
- 229920001690 polydopamine Polymers 0.000 claims description 34
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 32
- 229910000077 silane Inorganic materials 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 21
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims description 18
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 14
- 229920005646 polycarboxylate Polymers 0.000 claims description 14
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 13
- 230000035515 penetration Effects 0.000 claims description 13
- WSFMFXQNYPNYGG-UHFFFAOYSA-M dimethyl-octadecyl-(3-trimethoxysilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](OC)(OC)OC WSFMFXQNYPNYGG-UHFFFAOYSA-M 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 9
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 9
- 229920000053 polysorbate 80 Polymers 0.000 claims description 9
- 229940068968 polysorbate 80 Drugs 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003623 enhancer Substances 0.000 claims 2
- 239000004615 ingredient Substances 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 46
- 239000004567 concrete Substances 0.000 abstract description 24
- 239000011148 porous material Substances 0.000 abstract description 11
- 239000004570 mortar (masonry) Substances 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000004576 sand Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 239000011083 cement mortar Substances 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 238000006703 hydration reaction Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 230000036571 hydration Effects 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- UCPCFUUTIVUVHK-UHFFFAOYSA-M sodium 2-(dimethylaminodiazenyl)benzenesulfonate Chemical compound CN(N=NC1=C(C=CC=C1)S(=O)(=O)[O-])C.[Na+] UCPCFUUTIVUVHK-UHFFFAOYSA-M 0.000 description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- JCYPECIVGRXBMO-UHFFFAOYSA-N 4-(dimethylamino)azobenzene Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1 JCYPECIVGRXBMO-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010998 test method 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Chemical group CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Chemical group C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000009736 wetting Methods 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/02—Portland cement
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a chloride ion permeation resistant portland cement and a preparation method thereof, wherein the chloride ion permeation resistant portland cement comprises the following components in parts by weight: 30-45 parts of portland cement clinker, 10-20 parts of limestone, 5-15 parts of bentonite, 5-10 parts of fly ash, 1-5 parts of slag, 5-10 parts of calcined clay, 1-5 parts of gypsum, 1-5 parts of titanium dioxide and 10-20 parts of reinforcing agent. The invention can form a stable and compact hydrophobic film on the surface of a cement matrix, inhibit the diffusion and transmission of corrosive media in a pore channel, improve the fluidity of mortar and sand, save water and improve the chloride ion permeation resistance of the prepared concrete.
Description
Technical Field
The invention relates to the field of building materials, in particular to chloride ion permeation resistant portland cement and a preparation method thereof.
Background
The service life of common concrete buildings is required to be more than 50 years, in recent years, accidents that concrete structures fail prematurely or leave service in advance due to insufficient durability still occur frequently, huge economic loss is caused, and the pressure of engineering maintenance is correspondingly increased. The durability failure of the concrete structure is caused by the change of physical and chemical properties and geometric dimensions of the material of the concrete or the steel bar, so that the appearance of the concrete member is changed, the requirement of normal use cannot be met, the bearing capacity is degraded, and the safety of the whole structure is finally influenced. Among them, the most common and serious cause is corrosion by chloride corrosion. Improving the chloride ion resistance of concrete materials is an effective way. At present, the improvement of the performance of the gel material cement has attracted the extensive attention of researchers.
CN 110105021A discloses a Portland cement-based material with high crack resistance and super chloride ion corrosion resistance; the paint mainly comprises the following components in percentage by mass: 25-40% of portland cement, 30-40% of slag powder, 15-25% of low-activity cementing material, 5-9% of gypsum, 0.3-2% of nano silicon dioxide, 0.4-1.2% of polycarboxylate water reducing agent, 0.3-1.5% of polyether shrinkage reducing agent, 1-4% of redispersible latex powder, 2-7% of metakaolin and 0.5-2% of calcined hydrotalcite. The Portland cement-based material has good crack resistance and extremely strong chloride ion erosion resistance, the 3-day compressive strength is more than 28MPa, the 28-day compressive strength is more than 60MPa, the 28-day flexural strength is more than 8MPa, and the 28-day chloride ion erosion resistance coefficient is less than 0.5 multiplied by 10-12m2The chloride ion erosion resistance coefficient is less than 0.35 multiplied by 10 in 60 days-12m2And/s, the chloride ion curing rate is more than 60 percent.
CN 106431036A discloses a marine portland cement and a preparation method thereof, wherein the marine portland cement comprises the following components in percentage by mass: 18 to 50 percent of clinker, 30 to 60 percent of common mineral powder, 5 to 15 percent of superfine mineral powder, 0 to 20 percent of fly ash and 8 to 12 percent of gypsum. The marine Portland cement has excellent chlorine ion corrosion resistance and mechanical property, and the lowest 28d chloride ion permeability coefficient can reach 0.36 multiplied by 10-12m2And the 28-day compressive strength can exceed 55MPa, and the concrete is suitable for preparing high-strength, high-impermeability and high-erosion-resistance concrete for ocean engineering.
In the prior art, the anti-permeation effect on chloride ions is good, but the evaluation of the comprehensive performance of cement is often lacked. It is necessary to provide a portland cement which has good workability, high strength and resistance to chloride ion penetration.
Disclosure of Invention
The chloride ion permeation resistant portland cement in the prior art has the defects of complex preparation process, high energy consumption, large pollution and low performance of prepared concrete. In order to solve the defects, the invention adopts partial waste and conventional cement materials, and adds the reinforcing agent to construct the silicate cement with the resistance to the penetration of chloride ions.
The chloride ion permeation resistant portland cement comprises the following components in parts by weight: 30-45 parts of portland cement clinker, 10-20 parts of limestone, 5-15 parts of bentonite, 5-10 parts of fly ash, 1-5 parts of slag, 5-10 parts of calcined clay, 1-5 parts of gypsum, 1-5 parts of titanium dioxide and 10-20 parts of reinforcing agent.
The invention also provides a preparation method of the chloride ion permeation resistant portland cement, which comprises the following steps:
step 1, weighing raw materials according to a formula; mixing and grinding limestone, bentonite, slag, gypsum and titanium dioxide until the particle size is 20-50 mu m, preparing a fine powder mixed material, and calcining the fine powder mixed material at high temperature to prepare a fine powder clinker;
and 2, respectively grinding the portland cement clinker and the calcined clay until the particle size is 50-100 mu m, mixing the portland cement clinker and the calcined clay to prepare powder, adding the fine powder clinker prepared in the step 1, fly ash and a reinforcing agent into the powder, and uniformly mixing to prepare the chloride ion permeation resistant portland cement.
Preferably, the high-temperature calcination temperature in the step 1 is 1300-1700 ℃, and the calcination time is 20-80 min.
The preparation steps of the reinforcing agent are as follows, and the parts are all parts by weight:
s1, adding graphene oxide, polydopamine and tris hydrochloride into 60-80 wt% ethanol water solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 10-40 wt% ammonia water solution into the uniform solution, adjusting the pH value to 8-9, and performing ultrasonic dispersion treatment for 0.3-2 hours to prepare a suspension;
s2, mixing the suspension prepared in the step S1, tetraethoxysilane, isobutyl triethoxysilane, nonionic surfactant, dispersing agent and water; reacting for 1-3 hours under the conditions of stirring and heating, wherein the stirring speed is 100-500 r/min, the heating temperature is 30-50 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing the modified graphene silane solution prepared in the step S2, sodium p-dimethylaminoazobenzene sulfonate, a polycarboxylate ether water reducing agent and a 60-80 wt% ethanol water solution, and stirring for reaction for 0.3-2 hours at a stirring speed of 100-400 r/min to obtain a suspension; centrifuging the suspension for 20-60 min at the rotating speed of 10000-15000 r/min, collecting the centrifuged precipitate, and washing the precipitate for 1-3 times by using water and absolute ethyl alcohol respectively; drying and grinding the collected precipitate to obtain the reinforcing agent.
Preferably, in the step S1, the components are calculated by weight: 10-20 parts of graphene oxide, 1-3 parts of polydopamine, 1-5 parts of tris (hydroxymethyl) aminomethane hydrochloride and 300-600 parts of 60-80 wt% ethanol aqueous solution.
Preferably, in the step S2, the components are calculated by weight: 20-30 parts of the suspension prepared in the step S1, 5-10 parts of ethyl orthosilicate, 5-15 parts of isobutyltriethoxysilane, 0.1-2 parts of nonionic surfactant, 0.1-1 part of dispersing agent and 100-300 parts of water.
Preferably, the nonionic surfactant in step S2 is composed of the following substances by mass: the mass ratio of the fatty alcohol-polyoxyethylene ether to the polysorbate 80 is 1: (1-2).
Preferably, the dispersing agent in step S2 is composed of one or more of polyethylene glycol, polyethylene wax, magnesium stearate, and glyceryl tristearate.
Preferably, in the step S3, the components are calculated by weight: 40-80 parts of modified graphene silane solution, 1-5 parts of sodium p-dimethylaminoazobenzene sulfonate, 0.01-0.5 part of polycarboxylate ether water reducing agent and 100-150 parts of 60-80 wt% ethanol water solution.
Graphene Oxide (GO) is a novel carbon nanomaterial that is receiving attention for its excellent mechanical, electrical, and thermal properties. In the prior art, the addition of the graphene oxide can reduce the internal porosity of cement and improve the mechanical property and durability of mortar. The functional group of the graphene can provide active sites for crystal growth, and improve the hydration of cementMicrostructure in the process. The higher the dispersion degree of the graphene oxide in the cement matrix, the stronger the interface bonding force given by the C-S-H chemical bond generated by the graphene oxide. However, when graphene oxide is in an alkaline cement solution, carboxyl on the surface of the graphene oxide is easily subjected to Ca generated by cement hydration2+Crosslinking, which destabilizes the graphene oxide, causing it to solidify; further, the nucleation effect and the crack bridging effect of the cement-based composite material cannot be fully exerted, and the performance of the cement-based composite material cannot be positively influenced. Therefore, a method for reinforcing cement by using graphene still needs to be improved, and the dispersion of graphene oxide in the cement alkaline solution mainly comprises physical ultrasonic treatment, surfactant addition, chemical modification and the like. The repulsion force between graphene oxide layers is enhanced by utilizing a polycarboxylate ether water reducer (PCE) through a steric hindrance effect, so that graphene oxide and Ca are hindered2+The contact of (2) is a method of uniformly dispersing graphene oxide in a cement matrix, but the treatment effect of the method is not ideal.
According to the method, firstly, a polydopamine in-situ polymerization method is adopted to prepare the graphene oxide sheet, polydopamine is taken as a reactive monomer to be adsorbed on the graphene oxide sheet, and oxidative autopolymerization is carried out in an alkaline environment. The polydopamine contains various active groups such as amino, hydroxyl, indole and the like, and can react with an epoxy group of a graphene oxide sheet. More oxygen-containing functional groups such as carboxyl, hydroxyl and the like are grafted on the surface of graphene oxide, polydopamine molecules grafted on a graphene oxide sheet layer have good stretchability and space stability, the functional groups are easily combined with organic molecules in the modes of hydrogen bond, static electricity or pi-pi bond accumulation and the like, the polymerization of siloxane molecules is better promoted, the crosslinking of a silane system is improved, and the stability and reliability of a polymer can be remarkably improved by the polydopamine modified graphene oxide.
According to the invention, polydopamine modified graphene oxide is applied to silane polymerization, isobutyl triethoxysilane and tetraethoxysilane are grafted and condensed on graphene oxide by adopting a sol-gel method, and isobutyl triethoxysilane molecules and polydopamine molecules on the surface of graphene oxide mainly pass through NH2Condensation reaction with OH groupsAnd in the connection, the graphene oxide sheets and silane molecules are bridged to form an amorphous compact network structure in the solution, so that the connected cement paste is more stable, a compact polymer film is formed on the surface of a cement matrix, the cement paste has an effective protection effect on hydration products, and the surface weight loss rate of the cement sample treated by the modified silane emulsion is lowest. This is because the polydopamine modified graphene oxide can be combined with more siloxane molecular chains to form a more stable multi-layer hydrophobic space network structure on the surface of the cement hydration product. With the addition of the graphene oxide nanosheets, the workability of the cement paste is reduced, since the graphene oxide nanosheets have a large surface area and a large water requirement for surface wetting. In addition, the dispersion stability of the nanosheets in a cement environment is poor, so that serious agglomeration can be caused, free water is adsorbed, the fluidity is obviously reduced, and the performance of cement mortar is influenced. In a water-alcohol solution, condensation of tetraethoxysilane and proton functional groups such as hydroxyl, carboxyl and the like on the surface of graphene oxide can form a silicon dioxide coating layer on the surface of graphene oxide, the change of the surface charge of the silicon dioxide coating layer can be ignored, and the small change of the surface charge can be attributed to abundant hydroxyl on silicon dioxide. The grafting of the silicon dioxide covers a carboxyl functional group, and the coating of the silicon dioxide in the graphene oxide can effectively relieve the crosslinking of the graphene oxide. In addition, the silicon dioxide coating may act as a spacer on the graphene oxide, physically separating the graphene oxide and weakening van der waals forces. The strength of the prepared cement mortar is improved, and the enhanced compressive strength is probably due to the fact that the dispersibility of the graphene oxide is improved, and the negative effects of pores and stress concentration are reduced. The graphene oxide improves the adhesive force between the coating and the cement matrix through the pi-pi effect, and improves the density and the crack expansion resistance of the polymer.
On the other hand, Ca (OH)2The silicon hydroxyl group of the C-S-H gel structure and the hydroxyl group of the silane molecule are subjected to more direct reactions due to continuous consumption in the reaction with the silane molecule, and the integrity and the stability of a silicate network are also improved. The silane composite material can not only form a complete hydrophobic film on the surface and in the cement base, but also can penetrate into capillary pores and concretes of concreteAnd in the glue holes, diffusion and transmission of water and corrosive media in the pore channels are inhibited. The surface tension generated on the concrete surface is far lower than that of water and capillaries, so that the pores of the concrete capillaries are not blocked, and the normal air permeability of the concrete is kept. The grafting of silane in the graphene oxide can improve the molecular configuration and the space stability of a polymer system, and endow a polymer coating with excellent physical and chemical properties. The graphene oxide sheet not only can resist the diffusion and transportation of water and corrosive media in the polymer coating, but also can be used as a reaction platform to promote molecular polymerization. For the surface protection of porous heterogeneous materials such as concrete and the like, the modification of the graphene oxide can fully play the hydrophobicity of the isobutyl triethoxysilane, effectively improve the capability of resisting erosion ions, and further improve the durability of the concrete material.
Sodium p-dimethylaminoazobenzenesulfonate (C)14H14N3SO3Na) whose aromatic ring structure is similar to graphene oxide. Most importantly, the dye has wide application in the dyeing industry due to low production cost and good solubility in water. According to the characteristics, the sodium dimethylaminoazobenzenesulfonate is subjected to post-treatment, due to high hydrophobicity of pi electron carbon atoms in graphene oxide, a pi system of the graphene oxide and benzene rings in molecules of the sodium dimethylaminoazobenzenesulfonate are subjected to pi-pi interaction, the graphene oxide has physical adsorption capacity on the sodium dimethylaminoazobenzenesulfonate, and the sodium dimethylaminoazobenzenesulfonate can be adsorbed on a graphene oxide sheet layer in an alkaline environment, so that the distance between the graphene oxide sheet layers is increased, and the graphene oxide sheet layer is prevented from being aggregated. The surface of the sodium p-dimethylaminoazobenzenesulfonate is negatively charged, and Ca in the cement solution is reduced2+The concentration and partial hydrophilic functional groups can be adsorbed on the surface of unhydrated cement particles, and hydration shells with negative charges are formed outside the particles, so that the electrostatic repulsion between the connecting agents is enhanced, the retained free water is released, and the fluidity of the cement mortar is improved. The modified graphene oxide can promote and improve the structure of cement hydration products. The improvement effect depends to some extent on the degree of dispersion of the graphene oxide. Sodium salt of dimethylamino azobenzene sulfonic acidThe addition of the graphene oxide promotes the dispersion of the graphene oxide in the mortar, so that the graphene oxide has a larger regulation effect on the formation of hydration products and the formation of the hydration products is more compact.
The inventor finds in a large number of production practices that the polymerization of polydopamine on the surface of graphene oxide is faster in the initial reaction stage, easy to form aggregates in the initial stage, and further increases the mass after silane modification, so that the polydopamine is easy to delaminate in an aqueous solution, and limited in dispersibility in mixed cement slurry, and based on the effect of the large specific surface area of graphene, the polydopamine can be used as a template for formation of ettringite. In this way, the addition of the reinforcing agent has a risk that the local hydration action is too strong and cracks are easily generated. Therefore, the inventor conducts a large number of experiments, and finds that the strong effect at the initial stage of the reaction can be reduced, the agglomeration of the polydopamine can be reduced, the dispersion performance of the modifier in the mixed slurry can be enhanced, and the performance of the silicate cement can be further improved by adding a certain amount of 3- (trimethoxysilyl) propyl dimethyloctadecyl ammonium chloride in the graphene oxide polymerization process.
Further preferably, the preparation steps of the reinforcing agent are as follows:
s1, adding graphene oxide, polydopamine, tris (hydroxymethyl) aminomethane hydrochloride and 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride into a 60-80 wt% ethanol aqueous solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 10-40 wt% ammonia water solution into the uniform solution, adjusting the pH value to 8-9, and performing ultrasonic dispersion treatment for 0.3-2 hours to obtain a suspension;
s2, mixing the suspension prepared in the step S1, tetraethoxysilane, isobutyl triethoxysilane, nonionic surfactant, dispersing agent and water; reacting for 1-3 hours under the conditions of stirring and heating, wherein the stirring speed is 100-500 r/min, the heating temperature is 30-50 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing the modified graphene silane solution prepared in the step S2, sodium p-dimethylaminoazobenzene sulfonate, a polycarboxylate ether water reducing agent and a 60-80 wt% ethanol water solution, and stirring for reaction for 0.3-2 hours at a stirring speed of 100-400 r/min to obtain a suspension; centrifuging the suspension for 20-60 min at the rotating speed of 10000-15000 r/min, collecting the centrifuged precipitate, and washing the precipitate for 1-3 times by using water and absolute ethyl alcohol respectively; drying and grinding the collected precipitate to obtain the reinforcing agent.
Preferably, in the step S1, the components are calculated by weight: 10-20 parts of graphene oxide, 1-3 parts of polydopamine, 1-5 parts of tris (hydroxymethyl) aminomethane hydrochloride, 0.2-0.5 part of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and 300-600 parts of 60-80 wt% ethanol aqueous solution.
Preferably, in the step S2, the components are calculated by weight: 20-30 parts of the suspension prepared in the step S1, 5-10 parts of ethyl orthosilicate, 5-15 parts of isobutyltriethoxysilane, 0.1-2 parts of nonionic surfactant, 0.1-1 part of dispersing agent and 100-300 parts of water.
Preferably, the nonionic surfactant in step S2 is composed of the following substances by mass: the mass ratio of the fatty alcohol-polyoxyethylene ether to the polysorbate 80 is 1: (1-2).
Preferably, the dispersing agent in step S2 is composed of one or more of polyethylene glycol, polyethylene wax, magnesium stearate, and glyceryl tristearate.
Preferably, in the step S3, the components are calculated by weight: 40-80 parts of modified graphene silane solution, 1-5 parts of sodium p-dimethylaminoazobenzene sulfonate, 0.01-0.5 part of polycarboxylate ether water reducing agent and 100-150 parts of 60-80 wt% ethanol water solution.
Due to the adoption of the technical scheme, compared with the prior art, the preparation method of the chloride ion permeation resistant portland cement has the advantages that: 1) after the polydopamine is modified, isobutyl triethoxysilane and ethyl orthosilicate are grafted and condensed on graphene oxide, a stable and compact hydrophobic film can be formed on the surface of a cement matrix, diffusion and transmission of corrosive media in a pore channel are inhibited, the fluidity of mortar and sand is improved, water is saved, and the durability of the prepared concrete is improved. 2) The well-dispersed graphene oxide can promote the ordered arrangement of cement hydrated crystals, so that mortar forms a relatively compact structure, and the strength of prepared concrete is greatly improved. 3) The dimethylamino azobenzene sodium sulfonate is adsorbed on the graphene oxide sheet layer, so that the fluidity of the cement mortar is improved. 4) The synthesis process simply controls the use amounts of isobutyl triethoxysilane and ethyl orthosilicate, controls the silane content on the graphene oxide sheet, has good efficiency and controllability, and has feasibility of large-scale preparation.
Detailed Description
Sources of the main raw materials in the examples:
portland cement clinker: grade: grade a, xinglong county, fushui cement limited.
Slag: lingshou county Shi navigation building materials Co., Ltd.
Poly-dopamine: xi' an kangfuo biotechnology limited, particle size: 300 to 400 nm.
Tris hydrochloride salt: jiangsu Haolilong chemical industry, ltd, CAS no: 1185-53-1.
Ethyl orthosilicate: guangzhou double peach fine chemical Co., Ltd, molecular weight 208.33, CAS number: 78-10-4.
Isobutyl triethoxysilane: nanchang hongdun waterproof materials, Inc., appearance: clear liquid, CAS No.: 17980-47-1.
Sodium p-dimethylaminoazobenzenesulfonate: shenyang Saini Euro chemical Co., Ltd, molecular formula: c14H14N3NaO3S, CAS number: 547-58-0.
3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride, available from Shanghai Arlatin Biotech, Inc.
Example 1
The chloride ion permeation resistant portland cement consists of the following components in parts by weight: 36 parts of portland cement clinker, 15 parts of limestone, 10 parts of bentonite, 7 parts of fly ash, 3 parts of slag, 7 parts of calcined clay, 2 parts of gypsum, 2 parts of titanium dioxide and 16 parts of reinforcing agent.
The preparation method of the chloride ion permeation resistant portland cement comprises the following steps:
step 1, weighing raw materials according to a formula; mixing and grinding limestone, bentonite, slag, gypsum and titanium dioxide until the particle size is 30-40 mu m, preparing a fine powder mixed material, and calcining the fine powder mixed material at high temperature of 1500 ℃ for 60min to prepare fine powder clinker;
and 2, respectively grinding the portland cement clinker and the calcined clay until the particle size is 50-80 microns, mixing the portland cement clinker and the calcined clay to prepare powder, adding the fine powder clinker prepared in the step 1, fly ash and a reinforcing agent into the powder, and uniformly mixing to prepare the chloride ion permeation resistant portland cement.
The preparation steps of the reinforcing agent are as follows, and the parts are all parts by weight:
s1, adding 16 parts of graphene oxide, 2 parts of polydopamine and 3 parts of tris (hydroxymethyl) aminomethane hydrochloride into 400 parts of 70 wt% ethanol aqueous solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 25 wt% ammonia aqueous solution into the uniform solution, adjusting the pH value to 8.5, and performing ultrasonic dispersion treatment for 1 hour to prepare a suspension;
s2, mixing 25 parts of the suspension prepared in the step S1, 7 parts of ethyl orthosilicate, 10 parts of isobutyl triethoxysilane, 0.2 part of fatty alcohol-polyoxyethylene ether, 0.3 part of polysorbate 80, 0.5 part of polyethylene glycol and 200 parts of water; reacting for 2 hours under the conditions of stirring and heating, wherein the stirring speed is 300r/min, the heating temperature is 40 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing 60 parts of the modified graphene silane solution prepared in the step S2, 3 parts of sodium p-dimethylaminoazobenzene sulfonate, 0.1 part of polycarboxylate ether water reducer and 125 parts of 70 wt% ethanol water solution, and stirring for reaction for 1 hour at the stirring speed of 200r/min to obtain a suspension; centrifuging the suspension in a centrifuge at 12000r/min for 40min, collecting precipitate attached to the centrifuge tube, and washing with water and anhydrous ethanol for 2 times; drying and grinding the collected precipitate to obtain the reinforcing agent.
Example 2
A method for preparing a silicate cement resistant to chloride ion penetration is substantially the same as that of example 1, with the only difference that: the preparation method of the reinforcing agent is different.
The preparation method of the reinforcing agent in the embodiment comprises the following steps of:
s1, adding 16 parts of graphene oxide, 2 parts of polydopamine and 3 parts of tris (hydroxymethyl) aminomethane hydrochloride into 400 parts of 70 wt% ethanol aqueous solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 25 wt% ammonia aqueous solution into the uniform solution, adjusting the pH value to 8.5, and performing ultrasonic dispersion treatment for 1 hour to prepare a suspension;
s2, mixing 25 parts of the suspension prepared in the step S1, 10 parts of isobutyl triethoxysilane, 0.2 part of fatty alcohol-polyoxyethylene ether, 0.3 part of polysorbate 80, 0.5 part of polyethylene glycol and 200 parts of water; reacting for 2 hours under the conditions of stirring and heating, wherein the stirring speed is 300r/min, the heating temperature is 40 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing 60 parts of the modified graphene silane solution prepared in the step S2, 3 parts of sodium p-dimethylaminoazobenzene sulfonate, 0.1 part of polycarboxylate ether water reducer and 125 parts of 70 wt% ethanol water solution, and stirring for reaction for 1 hour at the stirring speed of 200r/min to obtain a suspension; centrifuging the suspension in a centrifuge at 12000r/min for 40min, collecting precipitate attached to the centrifuge tube, and washing with water and anhydrous ethanol for 2 times; drying and grinding the collected precipitate to obtain the reinforcing agent.
Example 3
A method for preparing a silicate cement resistant to chloride ion penetration is substantially the same as that of example 1, with the only difference that: the preparation method of the reinforcing agent is different.
The preparation method of the reinforcing agent in the embodiment comprises the following steps of:
s1, adding 16 parts of graphene oxide, 2 parts of polydopamine and 3 parts of tris (hydroxymethyl) aminomethane hydrochloride into 400 parts of 70 wt% ethanol aqueous solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 25 wt% ammonia aqueous solution into the uniform solution, adjusting the pH value to 8.5, and performing ultrasonic dispersion treatment for 1 hour to prepare a suspension;
s2, mixing 25 parts of the suspension prepared in the step S1, 7 parts of ethyl orthosilicate, 0.2 part of fatty alcohol-polyoxyethylene ether, 0.3 part of polysorbate 80, 0.5 part of polyethylene glycol and 200 parts of water; reacting for 2 hours under the conditions of stirring and heating, wherein the stirring speed is 300r/min, the heating temperature is 40 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing 60 parts of the modified graphene silane solution prepared in the step S2, 3 parts of sodium p-dimethylaminoazobenzene sulfonate, 0.1 part of polycarboxylate ether water reducing agent and 125 parts of 70 wt% ethanol water solution, and stirring for reaction for 1 hour at a stirring speed of 200r/min to obtain a suspension; centrifuging the suspension in a centrifuge at 12000r/min for 40min, collecting precipitate attached to the centrifuge tube, and washing with water and anhydrous ethanol for 2 times; drying and grinding the collected precipitate to obtain the reinforcing agent.
Example 4
A method for preparing a silicate cement resistant to chloride ion penetration is substantially the same as that of example 1, with the only difference that: the preparation method of the reinforcing agent is different.
The preparation method of the reinforcing agent in the embodiment comprises the following steps of:
s1, adding 16 parts of graphene oxide, 2 parts of polydopamine and 3 parts of tris (hydroxymethyl) aminomethane hydrochloride into 400 parts of 70 wt% ethanol aqueous solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 25 wt% ammonia aqueous solution into the uniform solution, adjusting the pH value to 8.5, and performing ultrasonic dispersion treatment for 1 hour to prepare a suspension;
s2, mixing 25 parts of the suspension prepared in the step S1, 7 parts of ethyl orthosilicate, 10 parts of isobutyl triethoxysilane, 0.2 part of fatty alcohol-polyoxyethylene ether, 0.3 part of polysorbate 80, 0.5 part of polyethylene glycol and 200 parts of water; reacting for 2 hours under the conditions of stirring and heating, wherein the stirring speed is 300r/min, the heating temperature is 40 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing 60 parts of the modified graphene silane solution prepared in the step S2, 0.1 part of polycarboxylate ether water reducer and 125 parts of 70 wt% ethanol water solution, and stirring for reaction for 1 hour at a stirring speed of 200r/min to obtain a suspension; centrifuging the suspension in a centrifuge at 12000r/min for 40min, collecting precipitate attached to the centrifuge tube, and washing with water and anhydrous ethanol for 2 times; drying and grinding the collected precipitate to obtain the reinforcing agent.
Example 5
A method for preparing the chloride ion penetration resistant portland cement is basically the same as that in example 1, and only the following differences are included: the preparation method of the reinforcing agent is different.
The preparation method of the reinforcing agent in the embodiment comprises the following steps of:
s1, adding 16 parts of graphene oxide, 2 parts of polydopamine, 3 parts of tris (hydroxymethyl) aminomethane hydrochloride and 0.2 part of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride into 400 parts of 70 wt% ethanol aqueous solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 25 wt% ammonia aqueous solution into the uniform solution, adjusting the pH value to 8.5, and performing ultrasonic dispersion treatment for 1 hour to obtain a suspension;
s2, mixing 25 parts of the suspension prepared in the step S1, 7 parts of ethyl orthosilicate, 10 parts of isobutyl triethoxysilane, 0.2 part of fatty alcohol-polyoxyethylene ether, 0.3 part of polysorbate 80, 0.5 part of polyethylene glycol and 200 parts of water; reacting for 2 hours under the conditions of stirring and heating, wherein the stirring speed is 300r/min, the heating temperature is 40 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing 60 parts of the modified graphene silane solution prepared in the step S2, 0.1 part of polycarboxylate ether water reducer and 125 parts of 70 wt% ethanol water solution, and stirring for reaction for 1 hour at a stirring speed of 200r/min to obtain a suspension; centrifuging the suspension in a centrifuge at 12000r/min for 40min, collecting precipitate attached to the centrifuge tube, and washing with water and anhydrous ethanol for 2 times; drying and grinding the collected precipitate to obtain the reinforcing agent.
Comparative example 1
A method for preparing the chloride ion penetration resistant portland cement is basically the same as that in example 1, and only the following differences are included: the preparation method of the reinforcing agent is different.
The preparation method of the reinforcing agent in the embodiment comprises the following steps of:
s1, adding 16 parts of graphene oxide, 2 parts of polydopamine and 3 parts of tris (hydroxymethyl) aminomethane hydrochloride into 400 parts of 70 wt% ethanol aqueous solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 25 wt% ammonia aqueous solution into the uniform solution, adjusting the pH value to 8.5, and performing ultrasonic dispersion treatment for 1 hour to prepare a suspension;
s2, mixing 25 parts of the suspension prepared in the step S1, 0.2 part of fatty alcohol-polyoxyethylene ether, 0.3 part of polysorbate 80, 0.5 part of polyethylene glycol and 200 parts of water; reacting for 2 hours under the conditions of stirring and heating, wherein the stirring speed is 300r/min, the heating temperature is 40 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing 60 parts of the modified graphene silane solution prepared in the step S2, 3 parts of sodium p-dimethylaminoazobenzene sulfonate, 0.1 part of polycarboxylate ether water reducer and 125 parts of 70 wt% ethanol water solution, and stirring for reaction for 1 hour at the stirring speed of 200r/min to obtain a suspension; centrifuging the suspension in a centrifuge at 12000r/min for 40min, collecting precipitate attached to the centrifuge tube, and washing with water and anhydrous ethanol for 2 times; drying and grinding the collected precipitate to obtain the reinforcing agent.
Comparative example 2
A portland cement is prepared by the same method as in example 1, with the only difference that: no reinforcing agent was added.
Test example 1
Water usage test for standard consistency
In order to test the influence of each example and comparative example on the water consumption of the standard consistency of the cement, the water consumption of the standard consistency of the portland cement and the cone sinking depth are tested according to GB/T1346-2011 inspection method for water consumption, setting time and stability of the standard consistency of the cement, and the influence of different preparation methods on the water consumption of the standard consistency of the portland cement prepared by the method is further analyzed. The test results are shown in Table 1.
Test example 2
Coagulation time test
The setting time of the portland cement is tested according to GB/T1346-2011 cement standard consistency water consumption, setting time and stability test method, and the setting time of the portland cement prepared in the examples and the portland cement prepared in the comparative example are measured under the condition of the same water consumption. The test results are shown in Table 1.
Test example 3
Cement paste fluidity test
The fluidity of the cement paste was measured according to GB/T8077-2012 "homogeneity test method for concrete admixtures" for determining the dispersion effect of the cement pastes of the examples and comparative examples, and is represented by the maximum diameter of the free flow of the cement paste on the glass plate. The test results are shown in Table 1.
Table 1: water consumption for standard consistency, net setting time and pulp fluidity test result
It can be seen from table 1 that the water consumption is the least, the setting time of cement is the longest, and the net slurry fluidity is the greatest in example 5, probably because graphene oxide has a large specific surface area and many oxygen-containing groups exist on the surface; the 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride can reduce the strong effect at the initial stage of the reaction, reduce the agglomeration of polydopamine and enhance the dispersion performance of the modifier in the mixed slurry. The large number of oxygen-containing groups makes graphene oxide highly hydrophilic and bonds to hydrogen atoms in water, and as the content of graphene oxide increases, more water is consumed. The dispersion stability of the single-component graphene oxide in a cement environment is poor, so that serious agglomeration can be caused, free water is absorbed, and the fluidity is obviously reduced. The graphene oxide sheet is prepared by a poly-dopamine in-situ polymerization method, poly-dopamine serving as a reactive monomer is adsorbed on the graphene oxide sheet, and oxidative self-polymerization is carried out in an alkaline environment. Introducing a plurality of active groups such as amino, hydroxyl, indole and the like to promote the polymerization of siloxane molecules, and grafting and condensing isobutyl triethoxysilane and tetraethoxysilane to graphene oxideIn the method, the isobutyltriethoxysilane molecules and the polydopamine molecules on the surface of the graphene oxide mainly pass through NH2The graphene oxide thin sheet is connected with OH groups through condensation reaction, the graphene oxide thin sheet and silane molecules are bridged, an amorphous compact network structure is formed in a solution, and the connected cement paste is more stable and shows the highest hydrophobicity; in a water-alcohol solution, tetraethoxysilane and proton functional groups such as hydroxyl, carboxyl and the like on the surface of graphene oxide undergo hydrolytic condensation. The grafting of the silicon dioxide covers carboxyl functional groups, a layer of silicon dioxide is coated in the graphene oxide, so that the crosslinking of the graphene oxide can be effectively relieved, the water consumption is reduced, the fluidity is increased, the integrity and the stability of a silicate network are enhanced by adding the dimethylamino azobenzene sodium sulfonate, and the processing of cement mortar is facilitated. Due to the high hydrophobicity of pi electron carbon atoms in the graphene oxide, a pi system of the graphene oxide and a benzene ring in molecules of the sodium p-dimethylaminoazobenzene sulfonate have pi-pi interaction, the graphene oxide has physical adsorption capacity on the sodium p-dimethylaminoazobenzene sulfonate, and the sodium p-dimethylaminoazobenzene sulfonate can be adsorbed on a graphene oxide sheet layer in an alkaline environment, so that the distance between the graphene oxide sheet layers is increased, and the graphene oxide sheet layers are prevented from being agglomerated. The surface of the sodium p-dimethylaminoazobenzenesulfonate is negatively charged, and Ca in the cement solution is reduced2+The concentration enhances the electrostatic repulsion between the connecting agents, releases the retained free water, and improves the fluidity of the cement mortar.
Test example 4
Mortar Strength test
The cement mortar strength of the examples and the comparative examples was tested according to GB/T17671-1999 Cement mortar Strength test method, and the flexural strength and compressive strength of the cement mortar were tested for 3 days and 28 days, and the test results are shown in Table 2.
Table 2: mortar strength test results
From table 2, it can be seen that the flexural strength and compressive strength of example 5 are the best, probably because the poor dispersion stability of graphene oxide alone in the cement environment can cause severe agglomeration, which affects the strength of cement mortar. Preparing graphene oxide by adopting a poly-dopamine in-situ polymerization method, grafting more oxygen-containing functional groups such as carboxyl, hydroxyl and the like on the surface of the graphene oxide, combining the functional groups with organic molecules in the modes of hydrogen bond, static electricity or pi-pi bond accumulation and the like, and combining isobutyl triethoxysilane and tetraethoxysilane molecular chains on the graphene oxide to form a more stable multilayer hydrophobic space network structure on the surface of a cement hydration product; the 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride can reduce the strong effect at the initial stage of the reaction, reduce the agglomeration of polydopamine and enhance the dispersion performance of the modifier in the mixed slurry. And (3) performing hydrolytic condensation on the tetraethoxysilane and proton functional groups such as hydroxyl, carboxyl and the like on the surface of the graphene oxide. The silicon dioxide coating on the graphene oxide may act as a spacer, physically separating the graphene oxide and weakening van der waals forces. Isobutyltriethoxysilane improves the integrity and stability of the silicate network. The silane composite material can not only form a complete hydrophobic membrane on the surface and in the cement base, but also permeate into capillary pores and gel pores of concrete, and inhibit the diffusion and transmission of water and corrosive media in the pore channels. The surface tension generated on the surface of the waterproof concrete is far lower than that of water and capillaries, so that the pores of the concrete capillaries are not blocked, the normal ventilation of the concrete is kept, and the negative effects of pores and stress concentration are reduced. The addition of the sodium dimethylaminoazobenzene sulfonate further improves the fluidity of the cement mortar. The graphene oxide with good dispersibility can promote the growth of cement hydrated crystals without changing the composition of cement hydrated products, and the ordered arrangement in the crystals can greatly improve the strength of cement mortar, so that the mortar forms a relatively compact structure, and the flexural strength and compressive strength of the cement mortar are improved due to the regulation effect of the graphene oxide on the hydrated products.
Test example 5
According to the standard of a test method for the long-term performance and the durability of standard GB/T50082-2009 common concrete, the chloride ion penetration resistance of a cylindrical cement 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 3. The lower the penetration depth, the lower the permeability coefficient, the better the chloride ion resistance.
TABLE 3 resistance to chloride ion penetration
| Depth of penetration (mm) | Coefficient of permeability (10)-12m2/s) | |
| Example 1 | 12.6 | 1.05 |
| Example 5 | 5.8 | 0.67 |
| Comparative example 2 | 1834 | 3.61 |
As can be seen from the results in table 1, example 5 of the present invention is significantly stronger in the resistance to chloride ion permeation than example 1. This is probably because the polydopamine-modified graphene oxide promotes the crosslinking reaction of siloxane molecules, and improves the stability against chloride ion permeation; the aromatic ring structure of the reduced graphene effectively prevents the migration of ions, so that the permeability of chloride ions is always kept at a lower level; the surface modification of the polydopamine enhances the obstruction of the graphene oxide sheet to the transmission of water molecules; the 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride can reduce the strong effect at the initial stage of reaction, reduce the agglomeration of polydopamine, enhance the dispersion performance of the modifier in the mixed slurry, ensure that the combination is tighter, and obviously reduce the chloride ion permeability under the combined action.
Claims (7)
1. The chloride ion permeation resistant portland cement comprises the following components in parts by weight: 30-45 parts of portland cement clinker, 10-20 parts of limestone, 5-15 parts of bentonite, 5-10 parts of fly ash, 1-5 parts of slag, 5-10 parts of calcined clay, 1-5 parts of gypsum, 1-5 parts of titanium dioxide and 10-20 parts of reinforcing agent;
the preparation steps of the reinforcing agent are as follows:
s1, adding graphene oxide, polydopamine, tris (hydroxymethyl) aminomethane hydrochloride and 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride into a 60-80 wt% ethanol aqueous solution, performing ultrasonic dispersion treatment for 2 hours to obtain a uniform solution, adding 10-40 wt% ammonia water solution into the uniform solution, adjusting the pH value to 8-9, and performing ultrasonic dispersion treatment for 0.3-2 hours to obtain a suspension;
s2, mixing the suspension prepared in the step S1, tetraethoxysilane, isobutyl triethoxysilane, nonionic surfactant, dispersing agent and water; reacting for 1-3 hours under the conditions of stirring and heating, wherein the stirring speed is 100-500 r/min, the heating temperature is 30-50 ℃, and standing to room temperature to obtain a modified graphene silane solution;
s3, mixing the modified graphene silane solution prepared in the step S2, sodium p-dimethylaminoazobenzene sulfonate, a polycarboxylate ether water reducer and 60-80 wt% of ethanol water solution, and stirring for reaction for 0.3-2 hours at a stirring speed of 100-400 r/min to obtain a suspension; centrifuging the suspension for 20-60 min at the rotating speed of 10000-15000 r/min, collecting the centrifuged precipitate, and washing the precipitate for 1-3 times by using water and absolute ethyl alcohol respectively; drying and grinding the collected precipitate to obtain the reinforcing agent.
2. The chloride ion penetration resistant portland cement of claim 1, wherein the enhancer is prepared by the following components in part by weight in step S1: 10-20 parts of graphene oxide, 1-3 parts of polydopamine, 1-5 parts of tris (hydroxymethyl) aminomethane hydrochloride, 0.2-0.5 part of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and 300-600 parts of 60-80 wt% ethanol water solution.
3. The chloride ion penetration resistant portland cement of claim 1, wherein the enhancer is prepared from the following components in part by weight in step S2: 20-30 parts of the suspension prepared in the step S1, 5-10 parts of ethyl orthosilicate, 5-15 parts of isobutyltriethoxysilane, 0.1-2 parts of nonionic surfactant, 0.1-1 part of dispersing agent and 100-300 parts of water.
4. The chloride ion permeation resistant portland cement of claim 1, wherein the nonionic surfactant in step S2 is composed of the following substances by mass: the mass ratio of the fatty alcohol-polyoxyethylene ether to the polysorbate 80 is 1: (1-2).
5. The chloride ion permeation resistant portland cement of claim 1, wherein the dispersing agent in step S2 is one or more selected from polyethylene glycol, polyethylene wax, magnesium stearate, and glyceryl tristearate.
6. The chloride ion permeation resistant portland cement of claim 1, wherein the ingredients in step S3 are, in parts by weight: 40-80 parts of modified graphene silane solution, 1-5 parts of sodium p-dimethylaminoazobenzene sulfonate, 0.01-0.5 part of polycarboxylate ether water reducing agent and 100-150 parts of 60-80 wt% ethanol water solution.
7. The method for producing a chloride ion permeation resistant portland cement according to any one of claims 1 to 6, comprising the steps of:
step 1, weighing raw materials according to a formula; mixing and grinding limestone, bentonite, slag, gypsum and titanium dioxide until the particle size is 20-50 mu m, preparing a fine powder mixed material, and calcining the fine powder mixed material at high temperature to prepare a fine powder clinker;
and 2, respectively grinding the portland cement clinker and the calcined clay until the particle size is 50-100 mu m, mixing the portland cement clinker and the calcined clay to prepare powder, adding the fine powder clinker prepared in the step 1, fly ash and a reinforcing agent into the powder, and uniformly mixing to prepare the chloride ion permeation resistant portland cement.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116023088A (en) * | 2022-10-26 | 2023-04-28 | 青岛领军新型建材科技有限公司 | Corrosion-resistant curbstone and preparation method thereof |
| CN117142827A (en) * | 2023-10-31 | 2023-12-01 | 北京慕湖外加剂有限公司 | Corrosion-resistant concrete and high-corrosion-resistance prestressed concrete pipe pile and application |
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| US5626665A (en) * | 1994-11-04 | 1997-05-06 | Ash Grove Cement Company | Cementitious systems and novel methods of making the same |
| CN113214738A (en) * | 2021-05-13 | 2021-08-06 | 青岛理工大学 | Polydopamine-modified graphene oxide-modified silane emulsion and preparation method and application thereof |
| CN113896453A (en) * | 2021-10-27 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Modified graphene composite material and preparation method thereof, cement reinforcing agent and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5626665A (en) * | 1994-11-04 | 1997-05-06 | Ash Grove Cement Company | Cementitious systems and novel methods of making the same |
| CN113214738A (en) * | 2021-05-13 | 2021-08-06 | 青岛理工大学 | Polydopamine-modified graphene oxide-modified silane emulsion and preparation method and application thereof |
| CN113896453A (en) * | 2021-10-27 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Modified graphene composite material and preparation method thereof, cement reinforcing agent and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116023088A (en) * | 2022-10-26 | 2023-04-28 | 青岛领军新型建材科技有限公司 | Corrosion-resistant curbstone and preparation method thereof |
| CN117142827A (en) * | 2023-10-31 | 2023-12-01 | 北京慕湖外加剂有限公司 | Corrosion-resistant concrete and high-corrosion-resistance prestressed concrete pipe pile and application |
| CN117142827B (en) * | 2023-10-31 | 2024-02-23 | 北京慕湖外加剂有限公司 | Corrosion-resistant concrete and high-corrosion-resistance prestressed concrete pipe pile and application |
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