CN117417148A - Janus structure concrete reinforcing agent and preparation method and application thereof - Google Patents
Janus structure concrete reinforcing agent and preparation method and application thereof Download PDFInfo
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- CN117417148A CN117417148A CN202311251552.5A CN202311251552A CN117417148A CN 117417148 A CN117417148 A CN 117417148A CN 202311251552 A CN202311251552 A CN 202311251552A CN 117417148 A CN117417148 A CN 117417148A
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- 239000004567 concrete Substances 0.000 title claims abstract description 55
- 239000012744 reinforcing agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 7
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 claims description 7
- 239000001263 FEMA 3042 Substances 0.000 claims description 7
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 235000004515 gallic acid Nutrition 0.000 claims description 7
- 229940074391 gallic acid Drugs 0.000 claims description 7
- 229940075579 propyl gallate Drugs 0.000 claims description 7
- 235000010388 propyl gallate Nutrition 0.000 claims description 7
- 239000000473 propyl gallate Substances 0.000 claims description 7
- 235000015523 tannic acid Nutrition 0.000 claims description 7
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 7
- 229940033123 tannic acid Drugs 0.000 claims description 7
- 229920002258 tannic acid Polymers 0.000 claims description 7
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 claims description 5
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 claims description 5
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 claims description 5
- 229940074393 chlorogenic acid Drugs 0.000 claims description 5
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 claims description 5
- 235000001368 chlorogenic acid Nutrition 0.000 claims description 5
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000003623 enhancer Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229920000620 organic polymer Polymers 0.000 abstract description 5
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 239000008346 aqueous phase Substances 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 229920001477 hydrophilic polymer Polymers 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011372 high-strength concrete Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
- C04B24/425—Organo-modified inorganic compounds, e.g. organo-clays
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a Janus structure concrete reinforcing agent and a preparation method and application thereof, wherein the invention firstly generates nano silicon dioxide polymer composite material (SiO) through condensation reaction of organic polymer and silicon source 2 -R) suspension, secondly by complexing SiO with metal particles 2 -R suspension, creating a nanocrystalline core C-S-H growth environment, and controlling the size and performance of the crystal core by a macromolecule. The early strength and the later strength of the concrete are enhanced by the crystal nucleus effect and the small-size effect of the nanometer in the concrete. The surface of the nanoparticle is provided with a hydrophilic polymer material, and the material has quick migration and diffusion in a concrete system and has a promoting effect on strength improvement. The invention uses Fe 3+ Complexing organic polymer to form aqueous phase gel, wherein the gel controls the size and the performance of the C-S-H, so as to synthesize the Janus structure nanocomposite with excellent performance.
Description
Technical Field
The invention belongs to the technical field of concrete additives, and particularly relates to a Janus structure concrete reinforcing agent, a preparation method and application thereof.
Background
With the progress of concrete technology, the requirements of building structures on the strength of concrete are continuously raised, and the requirements are gradually extended to concrete additives. Currently, with the increase of the demand of high-strength concrete for various engineering projects such as railways, highways, subways and the like, higher demands are put forward on the early strength of the concrete in order to accelerate the construction progress.
However, some common methods for promoting early reinforcement of concrete may result in a decrease in the strength of the concrete at a later stage, and even shrinkage problems may occur, thereby affecting the durability thereof. Therefore, it has become particularly critical to develop materials that are suitable for high strength concrete and that can improve early and late strength of the concrete.
In order to enhance the early strength of concrete, common methods include adding inorganic early strength agents, applying ultra-fine powder, and using inorganic salt excitants. However, the use of inorganic salts may negatively affect the post strength of the concrete, and powder materials may be difficult to uniformly disperse during application, thereby affecting early strength. In addition, even if a polycarboxylic acid water reducer having early strength properties is synthesized, or a conventional polycarboxylic acid water reducer is mixed with an early strength agent, the obtained early strength effect is often not ideal.
Therefore, it becomes important to explore an additive capable of effectively enhancing the strength of concrete.
Disclosure of Invention
The invention aims to provide a Janus structure concrete reinforcing agent and a preparation method thereof, wherein the reinforcing agent is prepared by condensation reaction of an organic polymer and a silicon source to generate a nano silicon dioxide polymer composite material (SiO) 2 -R) suspension, siO being complexed by metal particles 2 -R suspension, creating a nanocrystalline core C-S-H growth environment, and controlling the size and performance of the crystal core by a macromolecule.
It is still another object of the present invention to provide the use of a Janus structural concrete enhancer for concrete.
The specific technical scheme of the invention is as follows:
the preparation method of the Janus structure concrete reinforcing agent comprises the following steps:
1) Synthesis of nanosilica Polymer composite (SiO) 2 -R) a suspension;
2) The nano silicon dioxide polymer composite material (SiO 2 -R) mixing the suspension with water, complexing agent and base as a primer;
3) Mixing an organic component R, a silicon source and water to obtain a material A; taking a calcium source and water as a material B;
4) And (3) dripping the material A and the material B into the base material, and after finishing dripping, preserving heat and adjusting the pH value to 9-12.
The step 1) is specifically as follows: mixing the organic component R, a silicon source and water, reacting, and aging to obtain the nano silicon dioxide polymer composite material (SiO 2 -R) a suspension;
in the step 1), the mass ratio of the water to the organic component R to the silicon source is 200:10-100:10-50; preferably 200:50:20, a step of;
in the step 1), the organic component R is selected from one or more of tannic acid, gallic acid, chlorogenic acid and propyl gallate;
in the step 1), the silicon source is selected from one or more of sodium metasilicate pentahydrate, sodium silicate, tetraethyl silicate and tetramethyl silicate;
in the step 1), the reaction refers to the water bath temperature of 30-50 ℃ and the stirring reaction is carried out for 1-5h; preferably 45 ℃, for 4 hours;
in the step 1), the aging refers to the water bath temperature of 10-20 ℃ and the aging time of 1-10 hours; preferably 15℃for 5 hours.
SiO can be used for nano silicon dioxide polymer composite material 2 R represents an organic part, wherein the R part is generally composed of one or more of tannic acid, gallic acid, chlorogenic acid and propyl gallate; siO in the structural formula 2 The silicon source is one or more of sodium metasilicate pentahydrate, sodium silicate, tetraethyl silicate and tetramethyl silicate. Hydroxyl on the R component promotes condensation reaction of a silicon source to generate the nano silicon dioxide polymer composite material SiO 2 -R。
In step 2), the nano silicon dioxide polymer composite material (SiO 2 -R) the mass ratio of suspension, water, complexing agent and base is: 50-200:240:2-10:1-10; preferably, the nano silica polymer composite (SiO 2 -R) the mass ratio of suspension, water, complexing agent and base is: 200:240:5:5, a step of;
preferably, in step 2), the nano silica polymer composite (SiO 2 Mixing the suspension with water at water bath temperature of 10-45deg.C, adding complexing agent, and adding alkali after 5-10 min;
in the step 2), the complexing agent is ferrous sulfate;
in the step 2), the alkali is NaOH aqueous solution with the mass concentration of 30%;
in the step 3), in the material A, the mass ratio of the organic component R to the silicon source to the water is 1-10:5-30:85; preferably, the organic component R, the silicon source and the water are in a mass ratio of 3:10:85;
the organic component R is selected from one or more of tannic acid, gallic acid, chlorogenic acid and propyl gallate;
the silicon source is selected from one or more of sodium metasilicate pentahydrate, sodium silicate, tetraethyl silicate and tetramethyl silicate;
the organic component R and the silicon source in the material A are the same as the organic component R and the silicon source in the base material.
In the step 3), in the material B, the mass ratio of the calcium source to the water is as follows: 15-25:85; preferably, the mass ratio of the calcium source to the water is: 15:85;
in the step 4), the material A and the material B are simultaneously dripped, wherein the material A is dripped for 180min, and the material B is dripped for 190min;
in the step 4), after the A, B material is added dropwise, the temperature is kept for 3 hours, and the pH value of the solution is adjusted to 9-12, preferably 9.5; the dripping temperature is 15-25 ℃, and after the dripping is completed, the heat preservation is carried out without additional heating.
In the step 4), after the pH value of the solution is regulated to 9-12, water is added to obtain the product meeting the requirement of solid content.
The Janus structure concrete reinforcing agent provided by the invention is prepared by adopting the method. The prepared Janus structure concrete reinforcing agent is Fe- (SiO) 2 -R) x (C-S-H-R) y The structural formula is shown in the specification, wherein R is an organic part, and the R part is one or more of tannic acid, gallic acid, chlorogenic acid and propyl gallate; siO in the structural formula 2 The silicon source is one or more of sodium metasilicate pentahydrate, sodium silicate, tetraethyl silicate and tetramethyl silicate; x represents 1-10, Y represents 1-10.
The invention provides an application of a Janus structure concrete reinforcing agent, which is used for concrete.
Compared with the prior art, the invention is different from other organic and inorganic reinforcing agents or compound reinforcing agents, and provides a concrete reinforcing agent with a Janus structure, wherein the concrete reinforcing agent with the Janus structure is a composite product of two nano particles, and the main molecular structure of the concrete reinforcing agent is thatFe-(SiO 2 -R) x (C-S-H-R) y The concrete reinforcing agent is synthesized by a two-step method. Firstly, the condensation reaction of organic polymer and silicon source is carried out to generate nano silicon dioxide polymer composite material (SiO) 2 -R) suspension, secondly by complexing SiO with metal particles 2 The R suspension builds a growing environment of the nanocrystal cores C-S-H, and synthesizes the nano concrete reinforcing agent Fe- (SiO) with Janus structure by controlling the size and the performance of the nanocrystal cores through the macromolecule 2 -R) x (C-S-H-R) y . The early strength and the later strength of the concrete are enhanced by the crystal nucleus effect and the small-size effect of the nanometer in the concrete. Different from the nanoparticle compounding technology, the reinforcing agent with the nanostructure has the consistency of reinforcing the strength of the concrete, ensures that the strength of the concrete is uniformly distributed, and is beneficial to improving the durability of the concrete. The surface of the nanoparticle is provided with a hydrophilic polymer material, and the material has quick migration and diffusion in a concrete system and has a promoting effect on strength improvement. The invention uses Fe 3+ Complexing organic polymer to form aqueous phase gel, wherein the gel controls the size and the performance of the C-S-H, so as to synthesize the Janus structure nanocomposite with excellent performance.
Detailed Description
The invention provides a preparation method of a Janus structure concrete reinforcing agent, which comprises the following steps:
1) Nano silicon dioxide polymer composite material (SiO) 2 -R) suspension synthesis:
200mL of deionized water is weighed in a 500mL beaker, 10-100g of organic component R and 10-50g of silicon source are weighed, then added into the beaker for mixing, ultrasonic treatment is carried out for 10min, so that the organic component R and the silicon source are uniformly dispersed in the beaker, the beaker is placed on a magnetic stirrer, the water bath temperature is 30-50 ℃, and stirring is carried out for 1-5h. After stirring, placing the beaker into a water bath kettle, aging for 1-10h at the temperature of 10-20 ℃, wherein the obtained solution is nano silicon dioxide polymer composite material (SiO) 2 -R) suspension.
2) Janus structure nano composite material Fe- (SiO) 2 -R) x (C-S-H-R) y Is synthesized by the following steps:
2-1) And (3) backing materials: 50-200g of nano silicon dioxide polymer composite material (SiO) is added into a 1L four-mouth glass bottle 2 -R) suspension, 240g of water, the water bath temperature being adjusted to 10-45 ℃ so that the suspension is uniformly dispersed in the solution; after the suspension is completely dispersed, 2-10g of ferrous sulfate and 1-10g of NaOH (30%) aqueous solution are sequentially added into a four-mouth bottle at intervals of 5-10 minutes;
2-2) configuration of A material: 1-10g of organic component R, 5-30g of silicon source and 85g of deionized water, and preparing a material B: 15-25g of calcium source and 85g of deionized water;
2-3) starting to dropwise add the prepared A, B material; dripping A for 180min and dripping B for 190min;
2-4) after the A, B material drop is completed, keeping the temperature for 3 hours, adjusting the pH value of the solution to 9-12, adding 305-516g of water, and ending the reaction.
The following are several preferred embodiments, which proceed as follows:
example 1
The preparation method of the Janus structure concrete reinforcing agent comprises the following steps:
1) Nano silicon dioxide polymer composite material (SiO) 2 -R) suspension synthesis:
200mL of deionized water is weighed in a 500mL beaker, 50g of tannic acid and 20g of sodium metasilicate pentahydrate are weighed, then added into the beaker for mixing, ultrasonic treatment is carried out for 10min, the mixture is uniformly dispersed in the beaker, the beaker is placed on a magnetic stirrer, the water bath temperature is 45 ℃, and stirring is carried out for 4h. After stirring, placing the beaker in a water bath kettle at 15 ℃ for aging for 5 hours, wherein the obtained solution is nano silicon dioxide polymer composite material (SiO 2 -R) suspension.
2) Janus structure nano composite material Fe- (SiO) 2 -R) x (C-S-H-R) y Is synthesized by the following steps:
2-1) primer: 200g of nano silica polymer composite material (SiO) was put into a 1L four-necked glass bottle 2 -R) suspension, 240g of water, the water bath temperature being adjusted to 25 ℃ so that the suspension is uniformly dispersed in the solution; after the suspension is completely dispersed, 5g of ferrous sulfate and 5g of NaOH (30%) aqueous solution are sequentially added into a four-mouth bottle, and the interval is 10 minutes;
2-2) configuration of A material: 3g of tannic acid, 10g of sodium metasilicate pentahydrate and 85g of deionized water, and preparing a material B: 15g of a calcium source and 85g of deionized water;
2-3) starting to dropwise add the prepared A, B material; dripping A for 180min and dripping B for 190min;
2-4) after the A, B material drop is completed, keeping the temperature for 3 hours, adjusting the pH value of the solution to 9.5, adding 405g of water, and ending the reaction.
Example 2
The preparation method of the Janus structure concrete reinforcing agent comprises the following steps:
1) Nano silicon dioxide polymer composite material (SiO) 2 -R) suspension synthesis:
200mL of deionized water was weighed into a 500mL beaker, 20g of gallic acid and 40g of tetraethyl silicate were weighed, then added into the beaker for mixing, and the mixture was sonicated for 10min to uniformly disperse the mixture in the beaker, the beaker was placed on a magnetic stirrer, and the water bath temperature was 40 ℃, and the mixture was stirred for 5h. After stirring, the beaker is placed in a water bath kettle, the temperature is 10 ℃, and the beaker is aged for 6 hours, and the obtained solution is nano silicon dioxide polymer composite material (SiO 2 -R) suspension.
2) Janus structure nano composite material Fe- (SiO) 2 -R) x (C-S-H-R) y Is synthesized by the following steps:
2-1) primer: into a 1L four-port glass bottle, 100g of nano silica polymer composite material (SiO 2 -R) suspension, 240g of water, the water bath temperature being adjusted to 35 ℃ so that the suspension is uniformly dispersed in the solution; after the suspension is completely dispersed, 5g of ferrous sulfate and 5g of NaOH (30%) aqueous solution are sequentially added into a four-mouth bottle, and the interval is 10 minutes;
2-2) configuration of A material: 6g of gallic acid, 15g of tetraethyl silicate and 85g of deionized water, and preparing a material B: 20g of a calcium source and 85g of deionized water;
2-3) starting to dropwise add the prepared A, B material; dripping A for 180min and dripping B for 190min;
2-4) after the A, B material drop is completed, keeping the temperature for 3 hours, adjusting the pH value of the solution to 10, adding 400g of water, and ending the reaction.
Example 3
The preparation method of the Janus structure concrete reinforcing agent comprises the following steps:
1) Nano silicon dioxide polymer composite material (SiO) 2 -R) suspension synthesis:
200mL of deionized water was weighed into a 500mL beaker, 60g of propyl gallate and 30g of tetramethyl silicate were weighed, then added into the beaker for mixing, sonicated for 10min to uniformly disperse in the beaker, the beaker was placed on a magnetic stirrer, the water bath temperature was 40 ℃, and stirring was performed for 5h. After stirring, the beaker is placed in a water bath kettle, the temperature is 20 ℃, and the beaker is aged for 6 hours, and the obtained solution is nano silicon dioxide polymer composite material (SiO 2 -R) suspension.
2) Janus structure nano composite material Fe- (SiO) 2 -R) x (C-S-H-R) y Is synthesized by the following steps:
2-1) primer: 200g of nano silica polymer composite material (SiO) was put into a 1L four-necked glass bottle 2 -R) suspension, 240g of water, the water bath temperature being adjusted to 25 ℃ so that the suspension is uniformly dispersed in the solution; after the suspension is completely dispersed, 6g of ferrous sulfate and 6g of NaOH (30%) aqueous solution are sequentially added into a four-mouth bottle, and 10 minutes are separated in the middle;
2-2) configuration of A material: propyl gallate 7g, tetramethyl silicate 22g and deionized water 85g, and the material B is prepared by the following steps: 25g of a calcium source and 85g of deionized water;
2-3) starting to dropwise add the prepared A, B material; dripping A for 180min and dripping B for 190min;
2-4) after the A, B material drop is completed, keeping the temperature for 3 hours, adjusting the pH value of the solution to 10, adding 500g of water, and ending the reaction.
The Janus structure concrete reinforcing agent prepared in the above example 1 was used for concrete, with addition amounts of 0.03%, 0.06% and 0.09%, respectively; the concrete strength was tested with reference to GB 8076-2008, and the compressive strength of the tested concrete and the reference concrete was tested and calculated according to GB/T50081. When the test piece is manufactured, the vibration table is used for vibrating for 15s-20s. The test piece precuring temperature is (20+/-3) DEG C. The composition of the concrete is shown in Table 1. The test results are shown in Table 2. The test performance results are shown in Table 1, with no additive added as a comparison.
TABLE 1 15L-C50 concrete mix
Table 2 compressive strength of concrete
The concrete reinforcing agent with the Janus structure is used for concrete, and the early strength and the later strength of the concrete are enhanced.
Claims (10)
1. The preparation method of the Janus structure concrete reinforcing agent is characterized by comprising the following steps of:
1) Synthesis of nanosilica Polymer composite (SiO) 2 -R) a suspension;
2) The nano silicon dioxide polymer composite material (SiO 2 -R) mixing the suspension with water, complexing agent and base as a primer;
3) Mixing an organic component R, a silicon source and water to obtain a material A; taking a calcium source and water as a material B;
4) And (3) dripping the material A and the material B into the base material, and after finishing dripping, preserving heat and adjusting the pH value to 9-12.
2. The preparation method according to claim 1, wherein the step 1) specifically comprises: mixing the organic component R, a silicon source and water, reacting, and aging to obtain the nano silicon dioxide polymer composite material (SiO 2 -R) suspension.
3. The method according to claim 2, wherein in step 1), the mass ratio of the water, the organic component R and the silicon source is 200:10-100:10-50.
4. A method according to claim 2 or 3, wherein in step 1), the organic component R is selected from one or more of tannic acid, gallic acid, chlorogenic acid, propyl gallate; the silicon source is selected from one or more of sodium metasilicate pentahydrate, sodium silicate, tetraethyl silicate and tetramethyl silicate.
5. The preparation method according to claim 2, wherein in the step 1), the reaction is carried out at a water bath temperature of 30-50 ℃ with stirring for 1-5 hours; the aging refers to water bath temperature of 10-20 ℃ and aging for 1-10 hours.
6. The method according to claim 1, wherein in step 2), the nano silica polymer composite (SiO 2 -R) the mass ratio of suspension, water, complexing agent and base is: 50-200:240:2-10:1-10.
7. The preparation method according to claim 1 or 6, wherein in the step 3), in the material A, the mass ratio of the organic component R, the silicon source and the water is 1-10:5-30:85; in the material B, the mass ratio of the calcium source to the water is as follows: 15-25:85.
8. the method according to claim 1 or 6, wherein in step 4), after the completion of the gob addition of A, B, the temperature is kept for 3 hours, and the pH of the solution is adjusted to 9 to 12.
9. A Janus structural concrete enhancer prepared by the method of any one of claims 1 to 8.
10. Use according to claim 9, for concrete.
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