CN116535129A - Preparation method and application of nano calcium silicate hydrate type super early strength agent - Google Patents
Preparation method and application of nano calcium silicate hydrate type super early strength agent Download PDFInfo
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- CN116535129A CN116535129A CN202310533132.XA CN202310533132A CN116535129A CN 116535129 A CN116535129 A CN 116535129A CN 202310533132 A CN202310533132 A CN 202310533132A CN 116535129 A CN116535129 A CN 116535129A
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- aqueous solution
- early strength
- strength agent
- calcium silicate
- silicate hydrate
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- 239000000378 calcium silicate Substances 0.000 title claims abstract description 64
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 64
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 239000007864 aqueous solution Substances 0.000 claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 56
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 48
- 239000004567 concrete Substances 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 44
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 38
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 30
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 12
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000004115 Sodium Silicate Substances 0.000 claims description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000008030 superplasticizer Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 5
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 14
- 230000036571 hydration Effects 0.000 abstract description 11
- 238000006703 hydration reaction Methods 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- -1 rare earth compounds Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method 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
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
-
- 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)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to the technical field of early strength agents, in particular to a preparation method and application of a nano calcium silicate hydrate type early strength agent, wherein the preparation method comprises the following steps: (1) Adding a polycarboxylate water reducer/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, regulating the pH value to 11.5-12, heating to 50-55 ℃, dropwise adding a calcium salt aqueous solution and a silicon salt aqueous solution into the reaction kettle while stirring under the protection of nitrogen, regulating the pH value to 12-12.5 after dropwise adding, sealing the reaction kettle, heating to 70-80 ℃, and continuing to stir at constant temperature for reaction; (2) Cooling to 40-50 ℃, regulating the pH value to 7-7.5, simultaneously dropwise adding a p-phenylenediamine aqueous solution and an ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen while stirring, continuing to stir at constant temperature for reaction after the dropwise adding is finished, cooling to room temperature, centrifugally washing, and freeze-drying to obtain the aqueous solution. The nano calcium silicate hydrate super early strength agent prepared by the method can accelerate the cement hydration rate and effectively improve the early strength of concrete.
Description
Technical Field
The invention relates to the technical field of early strength agents, in particular to a preparation method and application of a nano calcium silicate hydrate type super early strength agent.
Background
The efficient utilization of cement clinker for preparing low-carbon concrete meeting engineering needs and products thereof are one of important technical approaches for energy conservation and emission reduction in the cement concrete industry. However, the problem of low early strength of concrete has limited its use in engineering.
The main technical approach and mechanism for obtaining high early strength of cement-based materials are as follows:
(1) Mixing with inorganic early strength agent and cement C 3 The A mineral reacts to form ettringite, so that the early strength of the mortar concrete is improved, or mixed crystals are formed with the antifreezing agent at negative temperature, so that the antifreezing performance is improved.
(2) The alkanol organic early strength agent is doped to promote the dissolution of aluminum phase in cement and improve early strength. The disadvantage is that it may lead to a decrease in the post strength and flexural strength.
(3) The hydration process of cement and the pozzolan reaction are accelerated through steam curing or autoclaved curing. The technical method is mainly used for curing cement products.
The conventional early strength agent and the early strength water reducing agent have limited promotion effect on the strength development of the cement-based material from the hydration acceleration period to 24 hours. In recent years, the super early strength of nano calcium silicate hydrate is widely paid attention to domestic and foreign scholars. Nano hydrated calcium silicate through C 3 S hydration site, accelerate the hydration process in cement 3d, can make concrete 1d and 3d intensity reach blank sample 3d and 7d intensity respectively, improve the early strength effect of concrete and be showing, especially can promote prefabricated component hydration acceleration period after intensity increase, accelerate drawing of patterns and lifting by crane, reduce steam curing link.
Therefore, the nano calcium silicate hydrate crystal nucleus type early strength agent is developed, the power-assisted clinker cement is efficiently utilized, and the concrete and products have early strength and super early strength performance, and have important application value and practical significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a nano calcium silicate hydrate super-early strength agent, and the prepared nano calcium silicate hydrate super-early strength agent has small particle size and strong dispersibility, can effectively reduce nucleation potential barriers of hydration products C-S-H gel, has a plurality of nucleation sites, accelerates the cement hydration rate, and effectively improves the early strength of concrete.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the preparation process of nanometer calcium silicate hydrate as one kind of super early strength agent includes the following steps:
(1) Adding a polycarboxylate water reducer/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, adding a sodium hydroxide solution to adjust the pH value to 11.5-12, heating to 50-55 ℃, then dropwise adding a calcium salt aqueous solution and a silicon salt aqueous solution into the reaction kettle under the protection of nitrogen while stirring, adding the sodium hydroxide solution to adjust the pH value to 12-12.5 after the dropwise adding is finished, sealing the reaction kettle, heating to 70-80 ℃, and continuing to stir at constant temperature for reaction;
(2) Then cooling to 40-50 ℃, adding a dilute nitric acid solution to adjust the pH value to 7-7.5, simultaneously dropwise adding a p-phenylenediamine aqueous solution and an ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen while stirring, continuing to stir at constant temperature for reaction after the dropwise addition is finished, cooling to room temperature, and performing centrifugal washing and freeze drying to obtain the nano calcium silicate hydrate super early strength agent.
Preferably, in the step (1), the mass fraction of the polycarboxylate water reducer/lanthanum nitrate/cerium nitrate aqueous solution is 3-6%, the mass fraction of the lanthanum nitrate is 0.1-0.2%, and the mass fraction of the cerium nitrate is 0.05-0.15%.
Preferably, in the step (1), the preparation method of the polycarboxylate superplasticizer comprises the following steps: adding 160-180 parts of isobutylenol polyoxyethylene ether, 15-25 parts of methacrylic polyethylene glycol ether and 150-170 parts of water into a reactor, stirring and heating to 80-85 ℃ under the protection of nitrogen, and simultaneously dropwise adding a first mixed solution and a second mixed solution into the reactor, wherein the first mixed solution is prepared by mixing 40-50 parts of acrylic acid, 20-30 parts of maleic anhydride, 5-6 parts of sodium methacrylate, 2-3 parts of mercaptopropionic acid and 80-100 parts of water, and the second mixed solution is prepared by mixing 1.5-2 parts of ammonium persulfate and 30 parts of water; the dripping time is 3-4h, after the dripping is finished, the constant temperature stirring is continued for 5-6h, the temperature is reduced to below 50 ℃, and the pH value is regulated to 7-7.5 by sodium hydroxide solution; and then dialyzing and purifying to obtain the polycarboxylate superplasticizer.
Preferably, the number average molecular weight of the isobutylether is 2000-3000, and the number average molecular weight of the methacrylic polyethylene glycol ether is 1500-2000.
Preferably, in step (1), the ratio of the total molar amount of calcium salt added dropwise to the reaction vessel to the total molar amount of silicon salt added dropwise is from 1.1 to 1.5:1, a step of; the mass ratio of the polycarboxylate water reducer/lanthanum nitrate/cerium nitrate aqueous solution to the calcium salt aqueous solution is 1:0.3-0.5.
Preferably, in the step (1), the calcium salt aqueous solution is one of a calcium nitrate aqueous solution and a calcium chloride aqueous solution; the silicate aqueous solution is one of sodium silicate aqueous solution and potassium silicate aqueous solution; the mass fraction of the calcium salt aqueous solution is 5-10%, and the mass fraction of the silicon salt aqueous solution is 8-15%.
Preferably, in the step (2), the mass fraction of the p-phenylenediamine aqueous solution is 3-4%, the mass fraction of the ammonium persulfate aqueous solution is 0.5-1%, and the mole ratio of the p-phenylenediamine to the ammonium persulfate dropwise added into the reaction kettle is 1:0.5-0.7;
the mole ratio of the p-phenylenediamine added dropwise into the reaction kettle in the step (2) to the silicon salt added dropwise into the reaction kettle in the step (1) is 0.08-0.15:1.
preferably, in the step (1), dropwise adding the calcium salt aqueous solution and the silicon salt aqueous solution into the reaction kettle for 5-9 hours; the reaction time of continuous stirring is 150-180min;
in the step (2), the reaction is continuously stirred for 30-60min; and during centrifugal washing, washing is sequentially performed by adopting water and ethanol.
The invention also provides a nano calcium silicate hydrate super early strength agent which is prepared by the preparation method of the nano calcium silicate hydrate super early strength agent.
The invention also provides application of the nano calcium silicate hydrate type super early strength agent, in particular application of the nano calcium silicate hydrate type super early strength agent to preparation of concrete, wherein the preparation raw materials of the concrete comprise gel materials, and the addition amount of the nano calcium silicate hydrate type super early strength agent in the concrete is 0.7-1.8% of the mass of the gel materials.
The beneficial effects of the invention are as follows:
1. according to the invention, the poly-p-phenylene diamine is polymerized on the hydrated calcium silicate prepared in the step (1) in situ, the poly-p-phenylene diamine is adsorbed on the surface of the hydrated calcium silicate, the adsorption force is strong, and the intercalation enters the interlayer of the nano CSH hydrated calcium silicate, and due to the existence of benzene rings, stronger electrostatic repulsive force and larger steric hindrance can be generated, so that the agglomeration of nano hydrated calcium silicate particles is effectively prevented, the nano hydrated calcium silicate can keep higher and more stable dispersibility, the particle size of the nano hydrated calcium silicate is further reduced, and the specific surface area is improved, so that when the nano hydrated calcium silicate super-early strength agent is used for preparing concrete, a uniform and compact structure can be formed at the early stage of cement hydration.
2. When the nano calcium silicate hydrate super early strength agent is prepared, lanthanum nitrate and cerium nitrate are added into the polycarboxylate water reducer solution, and the formed nano calcium silicate hydrate has smaller particle size through the matching of the rare earth compounds, so that a plurality of nucleation sites can be formed to facilitate the nucleation growth of C-S-H gel during the preparation of concrete.
3. The polycarboxylate water reducer prepared by the method can be effectively adsorbed on the surface of nano calcium silicate hydrate and intercalated on the surface of nano calcium silicate hydrate, has a strong steric hindrance effect, and can enable the size of the prepared nano calcium silicate hydrate crystal nucleus to be small.
4. The nano calcium silicate hydrate super early strength agent prepared by the method has the average particle size of 60-110nm, has strong dispersibility, can effectively reduce the nucleation barrier of hydration product C-S-H gel when being applied to the preparation of concrete, has a plurality of nucleation sites, accelerates the cement hydration rate, and effectively improves the early strength of the concrete.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention relates to a method for preparing a nano calcium silicate hydrate super early strength agent, which comprises the following steps of:
(1) and (3) preparing the polycarboxylate water reducer I.
The preparation method of the polycarboxylate superplasticizer I comprises the following steps: 180 parts of isobutylenol polyoxyethylene ether (with the number average molecular weight of 2500), 25 parts of methacrylic polyethylene glycol ether (with the number average molecular weight of 1800) and 170 parts of water are added into a reactor, under the protection of nitrogen, after stirring and heating to 80 ℃, a first mixed solution and a second mixed solution are simultaneously added into the reactor in a dropwise manner, wherein the first mixed solution is prepared by mixing 45 parts of acrylic acid, 30 parts of maleic anhydride, 6 parts of sodium methacrylate, 2.5 parts of mercaptopropionic acid and 90 parts of water, and the second mixed solution is prepared by mixing 2 parts of ammonium persulfate and 30 parts of water; the dripping time is 4 hours, after the dripping is finished, the constant temperature stirring is continued for 5.5 hours, the temperature is reduced to below 50 ℃, and the pH value is regulated to 7-7.5 by sodium hydroxide solution; and then obtaining the polycarboxylate superplasticizer I after dialysis and purification.
(2) And (3) preparing the polycarboxylate water reducer II.
The preparation method of the polycarboxylate water reducer II comprises the following steps: 160-180 parts of isobutylenol polyoxyethylene ether (with the number average molecular weight of 2500), 20 parts of methacrylic polyethylene glycol ether (with the number average molecular weight of 1800) and 155 parts of water are added into a reactor, under the protection of nitrogen, after stirring and heating to 80 ℃, a first mixed solution and a second mixed solution are added into the reactor in a dropwise manner, wherein the first mixed solution is prepared by mixing 40 parts of acrylic acid, 25 parts of maleic anhydride, 5 parts of sodium methacrylate, 2 parts of mercaptopropionic acid and 80 parts of water, and the second mixed solution is prepared by mixing 1.5 parts of ammonium persulfate and 30 parts of water; the dripping time is 4 hours, after the dripping is finished, the constant temperature stirring is continued for 6 hours, the temperature is reduced to below 50 ℃, and the pH value is regulated to 7-7.5 by sodium hydroxide solution; and then obtaining the polycarboxylate superplasticizer II after dialysis and purification.
(3) And (3) preparing a polycarboxylate water reducer III.
The preparation method of the polycarboxylate superplasticizer III comprises the following steps: 160-180 parts of isobutylenol polyoxyethylene ether (with the number average molecular weight of 2500), 15 parts of methacrylic polyethylene glycol ether (with the number average molecular weight of 1800) and 150 parts of water are added into a reactor, under the protection of nitrogen, after stirring and heating to 85 ℃, a first mixed solution and a second mixed solution are added into the reactor in a dropwise manner, wherein the first mixed solution is prepared by mixing 50 parts of acrylic acid, 20 parts of maleic anhydride, 6 parts of sodium methacrylate, 3 parts of mercaptopropionic acid and 100 parts of water, and the second mixed solution is prepared by mixing 2 parts of ammonium persulfate and 30 parts of water; the dripping time is 3 hours, after the dripping is finished, the constant temperature stirring is continued for 5 hours, the temperature is reduced to below 50 ℃, and the pH value is regulated to 7-7.5 by sodium hydroxide solution; and then obtaining the polycarboxylate superplasticizer III after dialysis and purification.
Example 1:
the preparation process of nanometer calcium silicate hydrate as one kind of super early strength agent includes the following steps:
(1) Adding a polycarboxylate water reducer II/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, wherein the mass fraction of the polycarboxylate water reducer II is 5%, the mass fraction of lanthanum nitrate is 0.2%, and the mass fraction of cerium nitrate is 0.1%; adding sodium hydroxide solution to adjust the pH value to 12, heating to 55 ℃, and then under the protection of nitrogen, simultaneously dropwise adding 8% calcium nitrate aqueous solution and 13% sodium silicate aqueous solution into a reaction kettle under the condition of stirring for 8 hours; after the dripping is finished, adding sodium hydroxide solution to adjust the pH value to 12.5, sealing the reaction kettle, heating to 80 ℃, and continuing to stir at constant temperature for reaction for 180min.
In the above step, the ratio of the total molar amount of calcium nitrate added dropwise to the reaction vessel to the total molar amount of sodium silicate added dropwise was 1.3:1. the mass ratio of the polycarboxylate water reducer II/lanthanum nitrate/cerium nitrate aqueous solution to the calcium nitrate aqueous solution is 1:0.3.
(2) Then cooling to 50 ℃, adding a dilute nitric acid solution to adjust the pH value to 7.5, simultaneously dropwise adding a 4% p-phenylenediamine aqueous solution and a 0.8% ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen while stirring, continuing to stir at constant temperature for reaction for 50min after the dropwise addition is finished, cooling to room temperature, performing centrifugal washing (washing by sequentially adopting water and ethanol), and performing freeze drying to obtain the nano calcium silicate hydrate super early strength agent.
In the step (2), the molar ratio of p-phenylenediamine to ammonium persulfate dropwise added into the reaction kettle is 1:0.5; and the mole ratio of the p-phenylenediamine added dropwise into the reaction kettle in the step (2) to the sodium silicate added dropwise into the reaction kettle in the step (1) is 0.12:1.
example 2:
the preparation process of nanometer calcium silicate hydrate as one kind of super early strength agent includes the following steps:
(1) Adding a polycarboxylate water reducer I/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, wherein the mass fraction of the polycarboxylate water reducer I is 4%, the mass fraction of lanthanum nitrate is 0.2%, and the mass fraction of cerium nitrate is 0.15%; adding sodium hydroxide solution to adjust the pH value to 11.5, heating to 50 ℃, and then dropwise adding 5% calcium nitrate aqueous solution and 8% potassium silicate aqueous solution into a reaction kettle under the protection of nitrogen gas while stirring for 5 hours; after the dripping is finished, adding sodium hydroxide solution to adjust the pH value to 12, sealing the reaction kettle, heating to 80 ℃, and continuing to stir and react for 160min at constant temperature.
In the above step, the ratio of the total molar amount of calcium nitrate added dropwise to the reaction vessel to the total molar amount of potassium silicate added dropwise was 1.2:1. the mass ratio of the polycarboxylate water reducer I/lanthanum nitrate/cerium nitrate aqueous solution to the calcium nitrate aqueous solution is 1:0.5.
(2) Then cooling to 50 ℃, adding a dilute nitric acid solution to adjust the pH value to 7.5, simultaneously dropwise adding 3.5% by mass of p-phenylenediamine aqueous solution and 0.7% by mass of ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen, continuously stirring at constant temperature for reaction for 50min after the dropwise addition, cooling to room temperature, performing centrifugal washing (washing by sequentially adopting water and ethanol), and freeze-drying to obtain the nano calcium silicate hydrate type super early strength agent.
In the step (2), the molar ratio of p-phenylenediamine to ammonium persulfate dropwise added into the reaction kettle is 1:0.6; and the mole ratio of the p-phenylenediamine added dropwise into the reaction kettle in the step (2) to the potassium silicate added dropwise into the reaction kettle in the step (1) is 0.1:1.
example 3:
the preparation process of nanometer calcium silicate hydrate as one kind of super early strength agent includes the following steps:
(1) Adding a polycarboxylate water reducer II/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, wherein the mass fraction of the polycarboxylate water reducer II is 3%, the mass fraction of lanthanum nitrate is 0.2%, and the mass fraction of cerium nitrate is 0.15%; adding sodium hydroxide solution to adjust the pH value to 12, heating to 50 ℃, and then dropwise adding 8% calcium nitrate aqueous solution and 11% sodium silicate aqueous solution into a reaction kettle under the protection of nitrogen gas while stirring for 7h; after the dripping is finished, adding sodium hydroxide solution to adjust the pH value to 12.5, sealing the reaction kettle, heating to 70 ℃, and continuing to stir at constant temperature for reaction for 180min.
In the above step, the ratio of the total molar amount of calcium nitrate added dropwise to the reaction vessel to the total molar amount of sodium silicate added dropwise was 1.1:1. the mass ratio of the polycarboxylate water reducer II/lanthanum nitrate/cerium nitrate aqueous solution to the calcium nitrate aqueous solution is 1:0.4.
(2) Then cooling to 50 ℃, adding a dilute nitric acid solution to adjust the pH value to 7.5, simultaneously dropwise adding a 4% p-phenylenediamine aqueous solution and a 1% ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen while stirring, continuing to stir at constant temperature for reaction for 60min after the dropwise addition is finished, cooling to room temperature, performing centrifugal washing (washing by sequentially adopting water and ethanol), and performing freeze drying to obtain the nano calcium silicate hydrate super early strength agent.
In the step (2), the molar ratio of p-phenylenediamine to ammonium persulfate dropwise added into the reaction kettle is 1:0.55; and the mole ratio of the p-phenylenediamine added dropwise into the reaction kettle in the step (2) to the sodium silicate added dropwise into the reaction kettle in the step (1) is 0.12:1.
example 4:
the preparation process of nanometer calcium silicate hydrate as one kind of super early strength agent includes the following steps:
(1) Adding a polycarboxylate water reducer III/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, wherein the mass fraction of the polycarboxylate water reducer III is 5%, the mass fraction of lanthanum nitrate is 0.15%, and the mass fraction of cerium nitrate is 0.05%; adding sodium hydroxide solution to adjust the pH value to 11.5, heating to 55 ℃, and then dropwise adding 10% calcium chloride aqueous solution and 15% sodium silicate aqueous solution into a reaction kettle under the protection of nitrogen gas while stirring for 9h; after the dripping is finished, adding sodium hydroxide solution to adjust the pH value to 12.5, sealing the reaction kettle, heating to 75 ℃, and continuing to stir at constant temperature for reaction for 150min.
In the above step, the ratio of the total molar amount of calcium chloride added dropwise to the reaction vessel to the total molar amount of sodium silicate added dropwise was 1.5:1. the mass ratio of the polycarboxylate water reducer III/lanthanum nitrate/cerium nitrate aqueous solution to the calcium chloride aqueous solution is 1:0.35.
(2) Then cooling to 40 ℃, adding a dilute nitric acid solution to adjust the pH value to 7, simultaneously dropwise adding 3.5% by mass of p-phenylenediamine aqueous solution and 0.5% by mass of ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen, continuously stirring at constant temperature for reaction for 30min after the dropwise addition, cooling to room temperature, performing centrifugal washing (washing by sequentially adopting water and ethanol), and freeze-drying to obtain the nano calcium silicate hydrate super early strength agent.
In the step (2), the molar ratio of p-phenylenediamine to ammonium persulfate dropwise added into the reaction kettle is 1:0.5; and the mole ratio of the p-phenylenediamine added dropwise into the reaction kettle in the step (2) to the sodium silicate added dropwise into the reaction kettle in the step (1) is 0.08:1.
example 5:
the preparation process of nanometer calcium silicate hydrate as one kind of super early strength agent includes the following steps:
(1) Adding a polycarboxylate water reducer I/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, wherein the mass fraction of the polycarboxylate water reducer I is 6%, the mass fraction of lanthanum nitrate is 0.15%, and the mass fraction of cerium nitrate is 0.1%; adding sodium hydroxide solution to adjust the pH value to 11.5, heating to 55 ℃, and then dropwise adding 5% calcium nitrate aqueous solution and 8% sodium silicate aqueous solution into a reaction kettle under the protection of nitrogen gas while stirring for 6 hours; after the dripping is finished, adding sodium hydroxide solution to adjust the pH value to 12, sealing the reaction kettle, heating to 80 ℃, and continuing to stir at constant temperature for reaction for 170min.
In the above step, the ratio of the total molar amount of calcium nitrate added dropwise to the reaction vessel to the total molar amount of sodium silicate added dropwise was 1.3:1. the mass ratio of the polycarboxylate water reducer I/lanthanum nitrate/cerium nitrate aqueous solution to the calcium nitrate aqueous solution is 1:0.5.
(2) Then cooling to 50 ℃, adding a dilute nitric acid solution to adjust the pH value to 7.5, simultaneously dropwise adding 3% by mass of p-phenylenediamine aqueous solution and 0.8% by mass of ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen while stirring, continuing to stir at constant temperature for reaction for 50min after the dropwise addition, cooling to room temperature, performing centrifugal washing (washing by sequentially adopting water and ethanol), and performing freeze drying to obtain the nano calcium silicate hydrate super early strength agent.
In the step (2), the molar ratio of p-phenylenediamine to ammonium persulfate dropwise added into the reaction kettle is 1:0.7; and the mole ratio of the p-phenylenediamine added dropwise into the reaction kettle in the step (2) to the sodium silicate added dropwise into the reaction kettle in the step (1) is 0.15:1.
comparative example 1:
the preparation process of nanometer calcium silicate hydrate as one kind of super early strength agent includes the following steps:
adding a polycarboxylate water reducer II/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, wherein the mass fraction of the polycarboxylate water reducer II is 5%, the mass fraction of lanthanum nitrate is 0.2%, and the mass fraction of cerium nitrate is 0.1%; adding sodium hydroxide solution to adjust the pH value to 12, heating to 55 ℃, and then under the protection of nitrogen, simultaneously dropwise adding 8% calcium nitrate aqueous solution and 13% sodium silicate aqueous solution into a reaction kettle under the condition of stirring for 8 hours; after the dripping is finished, adding sodium hydroxide solution to adjust the pH value to 12.5, sealing the reaction kettle, heating to 80 ℃, and continuing to stir at constant temperature for reaction for 180min. And then cooling to room temperature, and performing centrifugal washing and freeze drying to obtain the nano calcium silicate hydrate super early strength agent.
In the above step, the ratio of the total molar amount of calcium nitrate added dropwise to the reaction vessel to the total molar amount of sodium silicate added dropwise was 1.3:1. the mass ratio of the polycarboxylate water reducer II/lanthanum nitrate/cerium nitrate aqueous solution to the calcium nitrate aqueous solution is 1:0.3.
comparative example 2:
the preparation process of nanometer calcium silicate hydrate as one kind of super early strength agent includes the following steps:
(1) Adding a polycarboxylate water reducer II aqueous solution into a reaction kettle, wherein the mass fraction of the polycarboxylate water reducer II is 5%; adding sodium hydroxide solution to adjust the pH value to 12, heating to 55 ℃, and then under the protection of nitrogen, simultaneously dropwise adding 8% calcium nitrate aqueous solution and 13% sodium silicate aqueous solution into a reaction kettle under the condition of stirring for 8 hours; after the dripping is finished, adding sodium hydroxide solution to adjust the pH value to 12.5, sealing the reaction kettle, heating to 80 ℃, and continuing to stir at constant temperature for reaction for 180min.
In the above step, the ratio of the total molar amount of calcium nitrate added dropwise to the reaction vessel to the total molar amount of sodium silicate added dropwise was 1.3:1. the mass ratio of the polycarboxylate water reducer II aqueous solution to the calcium nitrate aqueous solution is 1:0.3.
(2) Then cooling to 50 ℃, adding a dilute nitric acid solution to adjust the pH value to 7.5, simultaneously dropwise adding a 4% p-phenylenediamine aqueous solution and a 0.8% ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen while stirring, continuing to stir at constant temperature for reaction for 50min after the dropwise addition is finished, cooling to room temperature, performing centrifugal washing (washing by sequentially adopting water and ethanol), and performing freeze drying to obtain the nano calcium silicate hydrate super early strength agent.
In the step (2), the molar ratio of p-phenylenediamine to ammonium persulfate dropwise added into the reaction kettle is 1:0.5; and the mole ratio of the p-phenylenediamine added dropwise into the reaction kettle in the step (2) to the sodium silicate added dropwise into the reaction kettle in the step (1) is 0.12:1.
performance test:
the nano calcium silicate hydrate type super early strength agent in the examples 1-5 and the comparative examples 1-2 is adopted to prepare concrete, so as to obtain concrete 1-7, wherein the concrete 1-7 comprises the following raw materials in parts by weight: 500 parts of P.52.5-grade ordinary Portland cement, 1200 parts of gravels (the particle size is 5-20 mm), 1000 parts of river sand (the fineness modulus is 2.6), 6 parts of polycarboxylate water reducer (water reducer I in the invention), 6 parts of nano calcium silicate hydrate super early strength agent and 190 parts of water. The above groups of concretes were then subjected to a compressive strength test and setting time test.
The compressive strength test of the concrete is carried out according to GB/T50081-2019 'test method Standard for physical and mechanical properties of concrete', the molding size of the concrete is 150mm multiplied by 150mm, and the concrete is placed in a standard curing room for curing, and the concrete test results are shown in Table 1.
Table 1 results of concrete compressive strength test
Concrete setting time test is carried out by referring to GB/T50080-2016 Standard for Performance test of common concrete mixtures, and specific test results are shown in Table 2.
Table 2 concrete setting time test results
| Super early strength agent | Initial setting time | Final setting time | |
| Concrete 1 | Example 1 | 3h20min | 6h |
| Concrete 2 | Example 2 | 3h | 5h40min |
| Concrete 3 | Example 3 | 3h40min | 6h30min |
| Concrete 4 | Example 4 | 3h30min | 6h30min |
| Concrete 5 | Example 5 | 3h20min | 5h50min |
| Concrete 6 | Comparative example 1 | 4h40min | 7h30min |
| Concrete 7 | Comparative example 2 | 4h20min | 7h |
As can be seen from tables 1 and 2, the use of the nano calcium silicate hydrate type super early strength agent of the present invention for preparing concrete can provide the obtained concrete with higher early strength and shorter setting time. As can be seen from comparison of concrete 1 and concrete 6-7, when the nano calcium silicate hydrate type super early strength agent is prepared, the early strength of the concrete can be improved and the setting time of the concrete can be shortened by adding lanthanum nitrate and cerium nitrate into the polycarboxylate water reducer solution and by in-situ polymerizing the poly-p-phenylene diamine on the calcium silicate hydrate prepared in the step (1).
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the nano calcium silicate hydrate type super early strength agent is characterized by comprising the following steps of:
(1) Adding a polycarboxylate water reducer/lanthanum nitrate/cerium nitrate aqueous solution into a reaction kettle, adding a sodium hydroxide solution to adjust the pH value to 11.5-12, heating to 50-55 ℃, then dropwise adding a calcium salt aqueous solution and a silicon salt aqueous solution into the reaction kettle under the protection of nitrogen while stirring, adding the sodium hydroxide solution to adjust the pH value to 12-12.5 after the dropwise adding is finished, sealing the reaction kettle, heating to 70-80 ℃, and continuing to stir at constant temperature for reaction;
(2) Then cooling to 40-50 ℃, adding a dilute nitric acid solution to adjust the pH value to 7-7.5, simultaneously dropwise adding a p-phenylenediamine aqueous solution and an ammonium persulfate aqueous solution into a reaction kettle under the protection of nitrogen while stirring, continuing to stir at constant temperature for reaction after the dropwise addition is finished, cooling to room temperature, and performing centrifugal washing and freeze drying to obtain the nano calcium silicate hydrate super early strength agent.
2. The method for preparing the nano calcium silicate hydrate super early strength agent according to claim 1, wherein in the step (1), the mass fraction of the polycarboxylate water reducer/lanthanum nitrate/cerium nitrate aqueous solution is 3-6%, the mass fraction of the lanthanum nitrate is 0.1-0.2%, and the mass fraction of the cerium nitrate is 0.05-0.15%.
3. The method for preparing the nano calcium silicate hydrate super early strength agent according to claim 1, wherein in the step (1), the method for preparing the polycarboxylate water reducer comprises the following steps: adding 160-180 parts of isobutylenol polyoxyethylene ether, 15-25 parts of methacrylic polyethylene glycol ether and 150-170 parts of water into a reactor, stirring and heating to 80-85 ℃ under the protection of nitrogen, and simultaneously dropwise adding a first mixed solution and a second mixed solution into the reactor, wherein the first mixed solution is prepared by mixing 40-50 parts of acrylic acid, 20-30 parts of maleic anhydride, 5-6 parts of sodium methacrylate, 2-3 parts of mercaptopropionic acid and 80-100 parts of water, and the second mixed solution is prepared by mixing 1.5-2 parts of ammonium persulfate and 30 parts of water; the dripping time is 3-4h, after the dripping is finished, the constant temperature stirring is continued for 5-6h, the temperature is reduced to below 50 ℃, and the pH value is regulated to 7-7.5 by sodium hydroxide solution; and then dialyzing and purifying to obtain the polycarboxylate superplasticizer.
4. The method for preparing nano calcium silicate hydrate super early strength agent according to claim 3, wherein the number average molecular weight of the isobutylether is 2000-3000, and the number average molecular weight of the methacrylic polyethylene glycol ether is 1500-2000.
5. The method for preparing nano calcium silicate hydrate super early strength agent according to claim 1, wherein in the step (1), the ratio of the total molar amount of calcium salt added dropwise to the reaction kettle to the total molar amount of silicon salt added dropwise is 1.1-1.5:1.
6. the method for preparing a nano calcium silicate hydrate type super early strength agent according to claim 1, wherein in the step (1), the calcium salt aqueous solution is one of a calcium nitrate aqueous solution and a calcium chloride aqueous solution; the silicate aqueous solution is one of sodium silicate aqueous solution and potassium silicate aqueous solution; the mass fraction of the calcium salt aqueous solution is 5-10%, and the mass fraction of the silicon salt aqueous solution is 8-15%.
7. The method for preparing the nano calcium silicate hydrate super early strength agent according to claim 1, wherein in the step (2), the mass fraction of the p-phenylenediamine aqueous solution is 3-4%, the mass fraction of the ammonium persulfate aqueous solution is 0.5-1%, and the molar ratio of the p-phenylenediamine to the ammonium persulfate added dropwise into the reaction kettle is 1:0.5-0.7;
the mole ratio of the p-phenylenediamine added dropwise into the reaction kettle in the step (2) to the silicon salt added dropwise into the reaction kettle in the step (1) is 0.08-0.15:1.
8. the method for preparing the nano calcium silicate hydrate super early strength agent according to claim 1, wherein in the step (1), the time for dropwise adding the calcium salt aqueous solution and the silicon salt aqueous solution into the reaction kettle is 5-9h; the reaction time of continuous stirring is 150-180min;
in the step (2), the reaction is continuously stirred for 30-60min; and during centrifugal washing, washing is sequentially performed by adopting water and ethanol.
9. A nano calcium silicate hydrate super early strength agent, which is prepared by the preparation method of the nano calcium silicate hydrate super early strength agent according to any one of claims 1 to 8.
10. The application of the nano calcium silicate hydrate type super early strength agent according to claim 9, wherein the nano calcium silicate hydrate type super early strength agent is applied to the preparation of concrete, the preparation raw materials of the concrete comprise gel materials, and the addition amount of the nano calcium silicate hydrate type super early strength agent in the concrete is 0.7-1.8% of the mass of the gel materials.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515618A (en) * | 2011-11-30 | 2012-06-27 | 上海大学 | Slow release slump retaining polycarboxylate water reducer and preparation thereof |
| CN111253107A (en) * | 2020-01-19 | 2020-06-09 | 武汉理工大学 | Hydramine modified calcium silicate hydrate nano crystal nucleus early strength agent and preparation method thereof |
| CN114560646A (en) * | 2022-04-26 | 2022-05-31 | 石家庄市长安育才建材有限公司 | Ultra-high strength concrete admixture and preparation method thereof |
| CN114804709A (en) * | 2022-05-23 | 2022-07-29 | 广西科达建材化工有限公司 | Novel early strength agent of nano calcium silicate hydrate polycarboxylic acid and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515618A (en) * | 2011-11-30 | 2012-06-27 | 上海大学 | Slow release slump retaining polycarboxylate water reducer and preparation thereof |
| CN111253107A (en) * | 2020-01-19 | 2020-06-09 | 武汉理工大学 | Hydramine modified calcium silicate hydrate nano crystal nucleus early strength agent and preparation method thereof |
| CN114560646A (en) * | 2022-04-26 | 2022-05-31 | 石家庄市长安育才建材有限公司 | Ultra-high strength concrete admixture and preparation method thereof |
| CN114804709A (en) * | 2022-05-23 | 2022-07-29 | 广西科达建材化工有限公司 | Novel early strength agent of nano calcium silicate hydrate polycarboxylic acid and preparation method thereof |
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