CN113443851A - Composite solid nano-based early strength agent and preparation method thereof - Google Patents
Composite solid nano-based early strength agent and preparation method thereof Download PDFInfo
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- CN113443851A CN113443851A CN202110697913.3A CN202110697913A CN113443851A CN 113443851 A CN113443851 A CN 113443851A CN 202110697913 A CN202110697913 A CN 202110697913A CN 113443851 A CN113443851 A CN 113443851A
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- 239000007787 solid Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 20
- 229920005646 polycarboxylate Polymers 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 17
- 239000008030 superplasticizer Substances 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000000243 solution 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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 19
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 8
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000010276 construction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000011178 precast concrete Substances 0.000 description 4
- 238000004134 energy conservation Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000009417 prefabrication Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/308—Thermal decomposition of nitrates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B2103/14—Hardening accelerators
Abstract
The invention discloses a composite solid nano-based early strength agent and a preparation method thereof, wherein the composite solid nano-based early strength agent is formed by uniformly mixing the following three substances in percentage by mass: the composite solid nano-based early strength agent can obviously improve the early strength of concrete and simultaneously enhance the later strength, and the composite solid nano-based early strength agent and the preparation method thereof have the advantages of improved performance, good reinforcing effect and convenience in storage and long-distance transportation.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a composite solid nano-based early strength agent and a preparation method thereof.
Background
In recent years, with the rapid development of high-speed rails, subways and the like and the rapid popularization of assembly type buildings in China, the implementation of factory prefabrication and assembly construction of building components becomes a necessary trend for the development of the building industry. The prefabricated building method is that prefabricated concrete members are manufactured according to the regulations in a factory in advance and then transported to the site for mechanical assembly like assembling of parts into a machine. Compared with the traditional building industry, the prefabricated building has the advantages of short construction period, high production efficiency, difficulty in intervention of external factors, outstanding contribution to environmental protection and energy conservation, and accordance with the modern energy-saving and environment-friendly concept. The concept of green building, energy conservation and environmental protection is currently carried out, but the problems of serious waste of building materials, high resource consumption, low efficiency and the like of cast-in-place concrete in the building are increasingly prominent. The precast concrete well makes up the defects of cast-in-place concrete due to the characteristics of quick construction, high quality, green, energy conservation and the like.
In order to accelerate the construction of concrete, shorten the construction period, and make the modules turn over as quickly as possible during construction, the early strength of the precast concrete has to be further strengthened. If the effect of high turnover of mould just can be reached through the mode that improves early strength, not only can improve production efficiency, can also reduce the occupation of mould. The method undoubtedly provides a more efficient and economic production mode for component production enterprises, so that the production efficiency can be greatly improved, and the production cost can be well controlled. Steam curing is a curing mode which is usually adopted by a component factory for improving the early strength of precast concrete, the curing time of the precast concrete component is 20 hours, how to shorten the concrete steam pressing time through the adjustment of a water reducing agent is realized, and the steam curing method has great significance for improving the economic benefit and realizing green production.
The traditional method for improving the early strength of concrete is to compound inorganic salt or organic matter with early strength effect and perform steam curing, but has many problems, such as that the introduction of chloride ions easily causes rusting of reinforcing steel bars, the introduction of sulfate early strength agents causes alkali-aggregate reaction, the selectivity of alcamines to cement is high, and the early strength effect is limited. The new generation of nanocrystalline nucleus type early strength agent provides a nucleus type inducer for the early stage of cement hydration, and can reduce the nucleation barrier of early hydration products, so that the crystallization speed of the hydration products is accelerated, and the early strength is obviously improved. However, the early strength agent introduces a new problem, and the later strength loss is obviously increased, so the early strength agent is also popularized and applied in a large scale in the future.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a composite solid nano-based early strength agent and a preparation method thereof, has improved performance and good reinforcing effect, is convenient to store and transport for a long distance, and can effectively solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a composite solid nano-based early strength agent is prepared from the following components in parts by weight: solid early strength type polycarboxylic acid water reducing agent: 80-90 parts of mesoporous nano silicon dioxide: 5-15 parts of mesoporous nano alumina: 5-10 parts.
A preparation method of a compound solid nano early strength agent comprises the following steps:
(1) preparation of solid early-strength polycarboxylate superplasticizer
Adding 100 parts of prenyl polyoxyethylene ether macromonomer into a three-neck flask, and heating to 50-60 ℃;
after the polyether monomer is completely melted, respectively adding 2-5 parts of cinnamamide, 1-2 parts of sodium methallyl sulfonate, 0.5-1.5 parts of aliphatic mercaptan, 1.5-2.5 parts of oxidant and initiator, and then dropwise adding 5-7 parts of acrylic acid, wherein the dropwise adding time is controlled within 1.5-1.8 h;
after the dropwise addition is finished, reacting for 0.6-0.9h, finally adding 8-12 parts of alkali liquor for neutralization, pouring out, and naturally cooling to obtain the solid early-strength polycarboxylate superplasticizer;
(2) preparation of mesoporous nano-silica
4g of polyoxyethylene-polyoxypropylene-polyoxyethylene (F127), 20g of KCl and 4.8g of n-hexane were weighed out separately at 15 ℃ and then dissolved together in 50ml of concentrated hydrochloric acid and 240ml of H2Stirring the O mixed solution by a magnetic stirrer until the O mixed solution is completely dissolved;
then slowly dripping 20ml of tetraethoxysilane into the mixed solution at a constant speed, continuously stirring the mixed solution at the ambient temperature of 15 ℃ for 20 hours, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in a constant-temperature oven at 100 ℃ for crystallization, and taking out the reaction kettle after 24 hours to naturally cool the reaction kettle to the room temperature;
washing the cooled product for multiple times by using deionized water, washing and filtering the product by using absolute ethyl alcohol after the product is neutral, and drying the product for 24 hours at 80 ℃ to obtain a white powdery sample;
the white powder was treated with 45% by weight of H at 95 deg.C2SO4Refluxing for 20h to remove the template agent, washing with deionized water and ethanol, filtering, and drying to obtain mesoporous nano-silica FDU-12;
(3) preparation of mesoporous nano alumina
6.25g of Al (NO) are weighed out3)3·9H2Dissolving O in 40ml of alcohol, stirring by using a magnetic stirrer until the O is completely dissolved, adding the synthesized 2g of mesoporous silica FDU-12, and continuously stirring to be powdery in a sandwich beaker at the temperature of 60 ℃;
then transferring the powder sample into a muffle furnace, slowly heating the muffle furnace to 250 ℃ and keeping the temperature for 6 hours to fully thermally decompose nitrate, and carrying out secondary impregnation on the pyrolyzed sample;
3.13g of Al (NO) are weighed out3)3·9H2Dissolving O and the product obtained by the first impregnation in 30ml ethanol, and stirring to dry in a 60 ℃ sandwich beaker by using a magnetic stirrerAdding a certain amount of n-hexane and stirring to powder;
then transferring it into muffle furnace at 1 deg.C for min-1Heating to 450 ℃, preserving heat for 6 hours for crystallization treatment, and fully reacting the sample with 2M NaOH solution after the sample is cooled to completely remove the FDU-12 template;
then washing the sample to be neutral by using deionized water and ethanol, and finally drying the sample in an oven at 80 ℃ for 24 hours to obtain a final sample;
(4) and respectively putting the solid early-strength polycarboxylate superplasticizer, the mesoporous nano-silica and the mesoporous nano-alumina into a ball mill for full polishing and mixing, thereby preparing the composite solid nano-based early-strength agent.
Preferably, the average molecular weight of the prenyl polyoxyethylene ether macromonomer is 4000.
Preferably, the initiator is azobisisobutyronitrile and azobisisoheptonitrile, the mass ratio is 2:1, the initiator is added in three times, the azobisisobutyronitrile is respectively added when the reaction is initiated and the reaction is carried out for 1/3 time, and the azobisisoheptonitrile is added when the reaction is carried out for 2/3 time.
Preferably, the alkali liquor is a mixed liquor of triethanolamine and diethanolisopropanolamine in a mass ratio of 1: 2.
Compared with the prior art, the invention has the beneficial effects that: the composite solid nano early strength agent and the preparation method thereof have the following advantages:
1. the early-strength polycarboxylate superplasticizer is synthesized by polyether macromonomer TPEG with the molecular weight of 4000, so that the molecular structure of the early-strength polycarboxylate superplasticizer is in a comb-shaped structure with short main chain length and side chains, and the early-strength polycarboxylate superplasticizer has the characteristic of promoting cement hydration. Through molecular structure design, the early strength water reducing agent product synthesized by the polyether macromonomer has the characteristic of enabling concrete to be soft in state and easy to construct;
2. when the early-strength polycarboxylate superplasticizer is prepared, the initiator is added in a batch mode, the proper active center concentration is kept, the polymerization reaction is carried out stably, and the phenomenon that the polymerization is exploded midway due to too violent early-stage reaction is avoided, so that the polymerization failure is caused. When the reaction reaches the later stage, a certain amount of initiator is supplemented, so that the conversion rate of the monomer can be improved, and the performance of the product is further improved;
3. when the early-strength solid polycarboxylic acid water reducer is prepared and the pH value of the early-strength solid polycarboxylic acid water reducer is neutralized, the selected alkali liquor is a mixture of triethanolamine and diethanol monoisopropanolamine, so that the pH value of the early-strength solid polycarboxylic acid water reducer is neutralized, and the effects of early strength and later strength enhancement are achieved;
4. according to the invention, the nano mesoporous silica is prepared by a hydrothermal method, and the surface of the nano mesoporous silica has a large amount of silicon hydroxyl groups, so that the nano mesoporous silica can play roles in pozzolanic reaction, crystal nucleus effect, filling effect and the like in a cement-based material, can promote cement hydration, improve the bonding interface of cement paste and aggregate, refine and harden the microstructure of cement paste, and improve mechanical properties. In addition, the concrete has a special mesoporous cage-shaped spherical self-supporting structure, so that the problem that the slump of the concrete is reduced due to easy agglomeration of a simple nano material can be effectively solved.
The invention prepares nano mesoporous alumina on the basis of nano mesoporous silica, and the nano mesoporous alumina is compounded and applied to concrete and is mixed with Ca (OH) in cement paste2The reaction forms calcium aluminate with compact structure and high hardness, further enhances the strength of concrete, and simultaneously exerts the technical advantages of nano particle enhancement.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a composite solid nano-based early strength agent is prepared from the following components in parts by weight: solid early strength type polycarboxylic acid water reducing agent: 80 parts of mesoporous nano silicon dioxide: 5 parts of mesoporous nano alumina: 5 parts of the raw materials.
A preparation method of a compound solid nano early strength agent comprises the following steps:
(1) preparation of solid early-strength polycarboxylate superplasticizer
Adding 100 parts of prenyl polyoxyethylene ether macromonomer into a three-neck flask, wherein the average molecular weight of the prenyl polyoxyethylene ether macromonomer is 4000, and heating to 50 ℃;
after the polyether monomer is completely melted, respectively adding 2 parts of cinnamamide, 1 part of sodium methallyl sulfonate, 0.5 part of aliphatic mercaptan, 1.5 parts of oxidant and initiator, then dropwise adding 5 parts of acrylic acid, controlling the dropwise adding time within 1.5, wherein the initiator is azobisisobutyronitrile and azobisisoheptonitrile, the mass ratio is 2:1, the initiator is added for three times, the azobisisobutyronitrile is respectively added when the reaction is initiated and carried out for 1/3 time, and the azobisisoheptonitrile is added when the reaction is carried out for 2/3 time;
after the dropwise addition is finished, reacting for 0.6h, finally adding 8 parts of alkali liquor, neutralizing, pouring out, and naturally cooling to obtain the solid early-strength polycarboxylate water reducer, wherein the alkali liquor is a mixed solution of triethanolamine and diethanol monoisopropanolamine, and the mass ratio of the alkali liquor to the diethanol monoisopropanolamine is 1: 2;
(2) preparation of mesoporous nano-silica
4g of polyoxyethylene-polyoxypropylene-polyoxyethylene (F127), 20g of KCl and 4.8g of n-hexane were weighed out separately at 15 ℃ and then dissolved together in 50ml of concentrated hydrochloric acid and 240ml of H2Stirring the O mixed solution by a magnetic stirrer until the O mixed solution is completely dissolved;
then slowly dripping 20ml of tetraethoxysilane into the mixed solution at a constant speed, continuously stirring the mixed solution at the ambient temperature of 15 ℃ for 20 hours, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in a constant-temperature oven at 100 ℃ for crystallization, and taking out the reaction kettle after 24 hours to naturally cool the reaction kettle to the room temperature;
washing the cooled product for multiple times by using deionized water, washing and filtering the product by using absolute ethyl alcohol after the product is neutral, and drying the product for 24 hours at 80 ℃ to obtain a white powdery sample;
the white powder was treated with 45% by weight of H at 95 deg.C2SO4Refluxing for 20h to remove the template agent, and reusingWashing and filtering with deionized water and ethanol, and drying to obtain mesoporous nano-silica FDU-12;
(3) preparation of mesoporous nano alumina
6.25g of Al (NO) are weighed out3)3·9H2Dissolving O in 40ml of alcohol, stirring by using a magnetic stirrer until the O is completely dissolved, adding the synthesized 2g of mesoporous silica FDU-12, and continuously stirring to be powdery in a sandwich beaker at the temperature of 60 ℃;
then transferring the powder sample into a muffle furnace, slowly heating the muffle furnace to 250 ℃ and keeping the temperature for 6 hours to fully thermally decompose nitrate, and carrying out secondary impregnation on the pyrolyzed sample;
3.13g of Al (NO) are weighed out3)3·9H2Dissolving O and the finished product obtained by the first impregnation into 30ml of ethanol, stirring the mixture in a 60 ℃ interlayer beaker by using a magnetic stirrer, and then adding a certain amount of normal hexane to stir the mixture into powder;
then transferring it into muffle furnace at 1 deg.C for min-1Heating to 450 ℃, preserving heat for 6 hours for crystallization treatment, and fully reacting the sample with 2M NaOH solution after the sample is cooled to completely remove the FDU-12 template;
then washing the sample to be neutral by using deionized water and ethanol, and finally drying the sample in an oven at 80 ℃ for 24 hours to obtain a final sample;
(4) and respectively putting the solid early-strength polycarboxylate superplasticizer, the mesoporous nano-silica and the mesoporous nano-alumina into a ball mill for full polishing and mixing, thereby preparing the composite solid nano-based early-strength agent.
Example two:
a composite solid nano-based early strength agent is prepared from the following components in parts by weight: solid early strength type polycarboxylic acid water reducing agent: 85 parts of mesoporous nano silica: 10 parts of mesoporous nano alumina: 8 parts of a mixture;
a preparation method of a compound solid nano early strength agent comprises the following steps:
(1) preparation of solid early-strength polycarboxylate superplasticizer
Adding 100 parts of prenyl polyoxyethylene ether macromonomer into a three-neck flask, wherein the average molecular weight of the prenyl polyoxyethylene ether macromonomer is 4000, and heating to 55 ℃;
after the polyether monomer is completely melted, respectively adding 3 parts of cinnamamide, 1 part of sodium methallyl sulfonate, 1 part of aliphatic mercaptan, 2 parts of oxidant and initiator, then dropwise adding 6 parts of acrylic acid, controlling the dropwise adding time within 1.7h, wherein the initiator is azobisisobutyronitrile and azobisisoheptonitrile, the mass ratio is 2:1, the initiator is added for three times, the azobisisobutyronitrile is respectively added when the reaction is initiated and carried out for 1/3 time, and the azobisisoheptonitrile is added when the reaction is carried out for 2/3 time;
after the dropwise addition is finished, reacting for 0.7h, finally adding 10 parts of alkali liquor, neutralizing, pouring out, and naturally cooling to obtain the solid early-strength polycarboxylate water reducer, wherein the alkali liquor is a mixed solution of triethanolamine and diethanol monoisopropanolamine, and the mass ratio of the alkali liquor to the diethanol monoisopropanolamine is 1: 2;
(2) preparation of mesoporous nano-silica
4g of polyoxyethylene-polyoxypropylene-polyoxyethylene (F127), 20g of KCl and 4.8g of n-hexane were weighed out separately at 15 ℃ and then dissolved together in 50ml of concentrated hydrochloric acid and 240ml of H2Stirring the O mixed solution by a magnetic stirrer until the O mixed solution is completely dissolved;
then slowly dripping 20ml of tetraethoxysilane into the mixed solution at a constant speed, continuously stirring the mixed solution at the ambient temperature of 15 ℃ for 20 hours, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in a constant-temperature oven at 100 ℃ for crystallization, and taking out the reaction kettle after 24 hours to naturally cool the reaction kettle to the room temperature;
washing the cooled product for multiple times by using deionized water, washing and filtering the product by using absolute ethyl alcohol after the product is neutral, and drying the product for 24 hours at 80 ℃ to obtain a white powdery sample;
the white powder was treated with 45% by weight of H at 95 deg.C2SO4Refluxing for 20h to remove the template agent, washing with deionized water and ethanol, filtering, and drying to obtain mesoporous nano-silica FDU-12;
(3) preparation of mesoporous nano alumina
6.25g of Al (NO) are weighed out3)3·9H2Dissolving O in 40ml of alcohol, stirring by using a magnetic stirrer until the O is completely dissolved, adding the synthesized 2g of mesoporous silica FDU-12, and continuously stirring to be powdery in a sandwich beaker at the temperature of 60 ℃;
then transferring the powder sample into a muffle furnace, slowly heating the muffle furnace to 250 ℃ and keeping the temperature for 6 hours to fully thermally decompose nitrate, and carrying out secondary impregnation on the pyrolyzed sample;
3.13g of Al (NO) are weighed out3)3·9H2Dissolving O and the finished product obtained by the first impregnation into 30ml of ethanol, stirring the mixture in a 60 ℃ interlayer beaker by using a magnetic stirrer, and then adding a certain amount of normal hexane to stir the mixture into powder;
then transferring it into muffle furnace at 1 deg.C for min-1Heating to 450 ℃, preserving heat for 6 hours for crystallization treatment, and fully reacting the sample with 2M NaOH solution after the sample is cooled to completely remove the FDU-12 template;
then washing the sample to be neutral by using deionized water and ethanol, and finally drying the sample in an oven at 80 ℃ for 24 hours to obtain a final sample;
(4) and respectively putting the solid early-strength polycarboxylate superplasticizer, the mesoporous nano-silica and the mesoporous nano-alumina into a ball mill for full polishing and mixing, thereby preparing the composite solid nano-based early-strength agent.
Example three:
a composite solid nano-based early strength agent is prepared from the following components in parts by weight: solid early strength type polycarboxylic acid water reducing agent: 90 parts of mesoporous nano silica: 15 parts of mesoporous nano alumina: 10 parts.
A preparation method of a compound solid nano early strength agent comprises the following steps:
(1) preparation of solid early-strength polycarboxylate superplasticizer
Adding 100 parts of prenyl polyoxyethylene ether macromonomer into a three-neck flask, wherein the average molecular weight of the prenyl polyoxyethylene ether macromonomer is 4000, and heating to 60 ℃;
after the polyether monomer is completely melted, respectively adding 5 parts of cinnamamide, 2 parts of sodium methallyl sulfonate, 1.5 parts of aliphatic mercaptan, 2.5 parts of oxidant and initiator, then dropwise adding 7 parts of acrylic acid, controlling the dropwise adding time within 1.8h, wherein the initiator is azobisisobutyronitrile and azobisisoheptonitrile, the mass ratio is 2:1, the initiator is added in three times, the azobisisobutyronitrile is respectively added when the reaction is initiated and carried out for 1/3 time, and the azobisisoheptonitrile is added when the reaction is carried out for 2/3 time;
after the dropwise addition is finished, reacting for 0.9h, finally adding 12 parts of alkali liquor, neutralizing, pouring out, and naturally cooling to obtain the solid early-strength polycarboxylate superplasticizer, wherein the alkali liquor is a mixed solution of triethanolamine and diethanol monoisopropanolamine, and the mass ratio of the alkali liquor to the diethanol monoisopropanolamine is 1: 2;
(2) preparation of mesoporous nano-silica
4g of polyoxyethylene-polyoxypropylene-polyoxyethylene (F127), 20g of KCl and 4.8g of n-hexane were weighed out separately at 15 ℃ and then dissolved together in 50ml of concentrated hydrochloric acid and 240ml of H2Stirring the O mixed solution by a magnetic stirrer until the O mixed solution is completely dissolved;
then slowly dripping 20ml of tetraethoxysilane into the mixed solution at a constant speed, continuously stirring the mixed solution at the ambient temperature of 15 ℃ for 20 hours, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in a constant-temperature oven at 100 ℃ for crystallization, and taking out the reaction kettle after 24 hours to naturally cool the reaction kettle to the room temperature;
washing the cooled product for multiple times by using deionized water, washing and filtering the product by using absolute ethyl alcohol after the product is neutral, and drying the product for 24 hours at 80 ℃ to obtain a white powdery sample;
the white powder was treated with 45% by weight of H at 95 deg.C2SO4Refluxing for 20h to remove the template agent, washing with deionized water and ethanol, filtering, and drying to obtain mesoporous nano-silica FDU-12;
(3) preparation of mesoporous nano alumina
6.25g of Al (NO) are weighed out3)3·9H2Dissolving O in 40ml of alcohol, and stirring with a magnetic stirrerAfter the mesoporous silica FDU-12 is completely dissolved, 2g of the synthesized mesoporous silica FDU-12 is added, and the mixture is continuously stirred to be powdery in a sandwich beaker at the temperature of 60 ℃;
then transferring the powder sample into a muffle furnace, slowly heating the muffle furnace to 250 ℃ and keeping the temperature for 6 hours to fully thermally decompose nitrate, and carrying out secondary impregnation on the pyrolyzed sample;
3.13g of Al (NO) are weighed out3)3·9H2Dissolving O and the finished product obtained by the first impregnation into 30ml of ethanol, stirring the mixture in a 60 ℃ interlayer beaker by using a magnetic stirrer, and then adding a certain amount of normal hexane to stir the mixture into powder;
then transferring it into muffle furnace at 1 deg.C for min-1Heating to 450 ℃, preserving heat for 6 hours for crystallization treatment, and fully reacting the sample with 2M NaOH solution after the sample is cooled to completely remove the FDU-12 template;
then washing the sample to be neutral by using deionized water and ethanol, and finally drying the sample in an oven at 80 ℃ for 24 hours to obtain a final sample;
(4) and respectively putting the solid early-strength polycarboxylate superplasticizer, the mesoporous nano-silica and the mesoporous nano-alumina into a ball mill for full polishing and mixing, thereby preparing the composite solid nano-based early-strength agent.
Concrete tests were conducted comparing the examples of the present invention with ordinary water-reducing agents and commercially available early strength polycarboxylic acid water-reducing agents (comparative examples). The mechanical properties of the concrete are carried out according to the method specified in GB/T50081-2019 test method standards for physical and mechanical properties of the concrete, the concrete composition is shown in the following table 1, and the test results of the early strength agent concrete are shown in the following table 2:
table 1: concrete mixing ratio (kg/m)3)
TABLE 2 Performance testing of early Strength type polycarboxylate superplasticizers
As can be seen from Table 1, the water-reducing rate of the composite solid nano-based early strength agent prepared by the embodiment of the invention is slightly lower than that of a common water-reducing agent, and is equivalent to that of a commercially available early strength agent; the early strength performance of the product is superior to that of the commercial early strength agent, and the later strength is not lost.
Claims (5)
1. A compound solid nano-based early strength agent is characterized in that: the composite solid nano early strength agent is prepared from the following components in parts by weight: solid early strength type polycarboxylic acid water reducing agent: 80-90 parts of mesoporous nano silicon dioxide: 5-15 parts of mesoporous nano alumina: 5-10 parts.
2. A preparation method of a compound solid nano-based early strength agent is characterized by comprising the following steps:
(1) preparation of solid early-strength polycarboxylate superplasticizer
Adding 100 parts of prenyl polyoxyethylene ether macromonomer (TPEG) into a three-neck flask, and raising the temperature to 50-60 ℃;
after the polyether monomer is completely melted, respectively adding 2-5 parts of cinnamamide, 1-2 parts of sodium methallyl sulfonate, 0.5-1.5 parts of aliphatic mercaptan, 1.5-2.5 parts of oxidant and initiator, and then dropwise adding 5-7 parts of acrylic acid, wherein the dropwise adding time is controlled within 1.5-1.8 h;
after the dropwise addition is finished, reacting for 0.6-0.9h, finally adding 8-12 parts of alkali liquor for neutralization, pouring out, and naturally cooling to obtain the solid early-strength polycarboxylate superplasticizer;
(2) preparation of mesoporous nano-silica
4g of polyoxyethylene-polyoxypropylene-polyoxyethylene (F127), 20g of KCl and 4.8g of n-hexane were weighed out separately at 15 ℃ and then dissolved together in 50ml of concentrated hydrochloric acid and 240ml of H2Stirring the O mixed solution by a magnetic stirrer until the O mixed solution is completely dissolved;
then slowly dripping 20ml of tetraethoxysilane into the mixed solution at a constant speed, continuously stirring the mixed solution at the ambient temperature of 15 ℃ for 20 hours, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in a constant-temperature oven at 100 ℃ for crystallization, and taking out the reaction kettle after 24 hours to naturally cool the reaction kettle to the room temperature;
washing the cooled product for multiple times by using deionized water, washing and filtering the product by using absolute ethyl alcohol after the product is neutral, and drying the product for 24 hours at 80 ℃ to obtain a white powdery sample;
the white powder was treated with 45% by weight of H at 95 deg.C2SO4Refluxing for 20h to remove the template agent, washing with deionized water and ethanol, filtering, and drying to obtain mesoporous nano-silica FDU-12;
(3) preparation of mesoporous nano alumina
6.25g of Al (NO) are weighed out3)3·9H2Dissolving O in 40ml of alcohol, stirring by using a magnetic stirrer until the O is completely dissolved, adding the synthesized 2g of mesoporous silica FDU-12, and continuously stirring to be powdery in a sandwich beaker at the temperature of 60 ℃;
then transferring the powder sample into a muffle furnace, slowly heating the muffle furnace to 250 ℃ and keeping the temperature for 6 hours to fully thermally decompose nitrate, and carrying out secondary impregnation on the pyrolyzed sample;
3.13g of Al (NO) are weighed out3)3·9H2Dissolving O and the finished product obtained by the first impregnation into 30ml of ethanol, stirring the mixture in a 60 ℃ interlayer beaker by using a magnetic stirrer, and then adding a certain amount of normal hexane to stir the mixture into powder;
then transferring it into muffle furnace at 1 deg.C for min-1Heating to 450 ℃, preserving heat for 6 hours for crystallization treatment, and fully reacting the sample with 2M NaOH solution after the sample is cooled to completely remove the FDU-12 template;
then washing the sample to be neutral by using deionized water and ethanol, and finally drying the sample in an oven at 80 ℃ for 24 hours to obtain a final sample;
(4) and respectively putting the solid early-strength polycarboxylate superplasticizer, the mesoporous nano-silica and the mesoporous nano-alumina into a ball mill for full polishing and mixing, thereby preparing the composite solid nano-based early-strength agent.
3. The preparation method of the composite solid nano-based early strength agent according to claim 2, characterized in that: the average molecular weight of the prenyl polyoxyethylene ether macromonomer is 4000.
4. The preparation method of the composite solid nano-based early strength agent according to claim 2, characterized in that: the initiator is azobisisobutyronitrile and azobisisoheptonitrile, the mass ratio is 2:1, the initiator is added in three times, the azobisisobutyronitrile is respectively added when the reaction is initiated and the reaction is carried out for 1/3 time, and the azobisisoheptonitrile is added when the reaction is carried out for 2/3 time.
5. The preparation method of the composite solid nano-based early strength agent according to claim 2, characterized in that: the alkali liquor is a mixed liquor of triethanolamine and diethanolisopropanolamine in a mass ratio of 1: 2.
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