A kind of early strength high fluidity geopolymer grouting material and preparation method thereof

Abstract

The present invention belongs to the technical field of civil engineering materials, and provides an early-strength high-fluidity geopolymer grouting material and a preparation method thereof. First, by heat treatment and chemical regulation of fly ash and granulated blast furnace slag, a pre-reaction phase with high reactivity is generated to improve the efficiency of alkali-induced reaction; then, by preparing a lubricating particle dispersion, the synergistic effect of silane coupling agent and interface lubricating particles is utilized to enhance the uniform dispersion of particles; by adding ionic liquid and functionalized amide-based polymer, the high polarity, ion shielding effect and dissolution enhancement performance of ionic liquid are utilized to accelerate the dissolution and activation of aluminosilicate; at the same time, the amide-based polymer inhibits particle agglomeration and stabilizes the particle dispersion state through adsorption, and the two cooperate to form a lubricating layer in the slurry, reduce the slurry viscosity, improve fluidity, and further accelerate the generation of gel phase to improve the early strength of the material.

Description

Technical Field

[0001] The invention belongs to the technical field of civil engineering materials and relates to an early-strength high-fluidity geopolymer grouting material and a preparation method thereof. Background Art

[0002] With the development of the construction industry, grouting materials are increasingly being used in the construction industry, such as prefabricated buildings, prestressed concrete bridges, and grouting reinforcement of building structures. In recent years, geopolymers have been widely used as a new type of green inorganic gelling material because of their wide material sources, the main material is industrial waste, and they have high strength, excellent mechanical properties, and excellent corrosion resistance under the action of alkali activators. Geopolymers are usually inorganic gelling materials made from industrial waste slag rich in silicon and aluminates under the action of alkali activators. Grouting materials generally require high early strength, but this will reduce the fluidity of the grouting material. The Chinese patent application with publication number CN108424063A discloses a fly ash-based polymer high-strength grouting material and a preparation method thereof, including fly ash, silica ash, plant ash and other active materials as binders, and after being activated by alkali activators, a small amount of admixtures are used to prepare high-strength grouting materials with early strength, fast hardening, high fluidity, and micro-expansion. However, this material uses a large amount of alkali activator. Too much alkali activator will also increase the cost, consume energy during preparation, and produce CO 2 At the same time, the expansion agent used is UEA expansion agent, which mainly uses calcium aluminate as the main expansion source, and its expansion stress needs water curing to form. Therefore, it is necessary to develop a new type of high-performance grouting material to solve the shortcomings of low early strength and poor fluidity of the grouting material. Summary of the invention

[0003] In view of the shortcomings of the prior art, the purpose of the present invention is to provide an early-strength high-fluidity geopolymer grouting material and a preparation method thereof. First, fly ash and granulated blast furnace slag powder are mixed, supplemented with chemical components such as sodium sulfate and sodium phosphate, and heat-treated at a specific temperature to obtain an intermediate product with high reactivity. Through the interface modification of a silane coupling agent and the preparation process of lubricating particles, a stable lubricating particle dispersion is generated. The lubricating particles play a dual role of lubrication and dispersion in the slurry. Through the polymerization reaction of functionalized polymers and the introduction of ionic liquids, a multifunctional rheological agent is prepared to optimize the rheological properties of the slurry, thereby meeting the needs of actual production.

[0004] To achieve this object, the present invention adopts the following technical solutions:

[0005] In a first aspect, the present invention provides a method for preparing an early-strength high-fluidity geopolymer grouting material, the preparation method comprising:

[0006] Step A1, mixing fly ash and granulated blast furnace slag powder, and then adding sodium sulfate and sodium phosphate to prepare a dry powder mixture, heating the mixture to a first temperature, and keeping the temperature to obtain a pre-reaction active phase;

[0007] Step A2, adding triethylamine and then adding a silane mixed solution to a polyethylene glycol aqueous solution, adjusting the pH to 9 to obtain a lubricating precursor, adding the silane coupling agent mixed solution to an ethanol aqueous solution, adjusting the pH to 4, then adding the lubricating precursor to the ethanol aqueous solution, heating to a second temperature for reaction, obtaining lubricating particles after the reaction is completed, and then adding the lubricating particles to deionized water to obtain a lubricating particle dispersion;

[0008] Step A3, adding 5 g of N-vinylformamide, 4 g of 2-acrylamido-2-methylpropanesulfonic acid, 0.4 g of methacrylic acid and 1.3 g of dodecyl methacrylate to deionized water in sequence, adjusting the pH to 8, heating to a third temperature, adding an initiator under a nitrogen atmosphere, stirring and reacting, pouring the polymer dispersion into anhydrous ethanol after the reaction is completed, precipitating a polymer, washing and freeze-drying to obtain a product A, mixing a 1-ethyl-3-methylimidazolium tetrafluoroborate solution with the product A solution to obtain a rheological agent;

[0009] Step S1, mixing water glass and sodium hydroxide to obtain an alkali activator A, and mixing fly ash, granulated blast furnace slag powder and a pre-reaction active phase to obtain a powder;

[0010] Step S2, mixing and dispersing water, lubricating dispersion, rheological agent, water reducing agent, swelling agent, sodium citrate, sodium sulfate, sodium phosphate, sodium ethylenediaminetetraacetate, dispersible rubber powder, and defoaming agent to obtain a mixed solution, mixing alkaline activator A with the mixed solution to obtain alkaline activator B, and weighing sand and fiber according to the weight for later use;

[0011] Step S4, adding alkali activator B to the powder for an average of 3 times within 2n time, then stirring at the first stirring speed for n time, then adding sand and fiber and stirring at the first stirring speed for n time, then stirring at the second stirring speed for n time, stopping for 2n time after stirring evenly, and then stirring at the second stirring speed for 3n time to obtain an early-strength high-fluidity geopolymer grouting material.

[0012] Fly ash is mainly composed of glassy silica and alumina. Its internal structure is relatively stable and usually presents an amorphous or partially crystalline state. Due to its low chemical activity, it requires a highly alkaline environment or high temperature treatment to promote its dissolution when directly used; slag powder mainly contains amorphous calcium silicate (CS) components and a small amount of alumina and magnesium oxide. Compared with fly ash, slag powder is more active because there are more calcium ions in its amorphous structure, which can provide the calcium source required for the alkali-induced reaction. Fly ash provides a rich source of silicon and aluminum, while slag powder provides a calcium source. When the two are mixed, the complementary characteristics of the calcium, silicon, and aluminum components help to generate more complex hydration products, such as calcium aluminum silicate hydrate (CASH) and sodium aluminum silicate hydrate (NASH). At high temperatures of 450-500°C, sodium sulfate partially dissociates and releases sulfate ions, which react with calcium ions in slag to form calcium sulfate phases (such as gypsum, CaSO 4 ·2H 2 O or anhydrous calcium sulfate, CaSO 4 ), sodium ions can synergize with the aluminosilicate components in fly ash and slag to improve the subsequent alkali activation efficiency. As an intermediate mineral phase, the calcium sulfate phase promotes the dissolution and hydration reaction of slag in the subsequent alkali activation process. The calcium silicate (CS) phase in the slag will generate more calcium sulfate phases due to the presence of sulfate ions. This process promotes the dissolution of slag, because the presence of sulfate ions will destroy the stability of the calcium-based components in the slag, making it easier to release calcium ions. The calcium sulfate phase can be further dissolved under the action of the alkaline activator, releasing calcium ions and sulfate ions, thereby providing more calcium ion sources for the subsequent calcium aluminosilicate hydrate gel formation and optimizing the morphology of the gel. The presence of calcium sulfate significantly accelerates the formation of early calcium aluminosilicate hydrate gel because the calcium ion release rate is faster and can react quickly with the dissolved aluminosilicate components. In addition to participating in the formation of calcium sulfate, sulfate ions also optimize the microstructure of the final hydration product. Sulfate ions can regulate the formation process of calcium aluminum silicate hydrate gel, making it more uniform on a microscopic scale and reducing porosity. The uniformly distributed calcium aluminum silicate hydrate gel improves the density of the material, thereby enhancing the compressive strength. The calcium sulfate phase will expand slightly during the hydration reaction. This expansion effect can partially offset the shrinkage caused by water evaporation during the hardening process. The combination of sulfate ions and aluminate components may also generate a small amount of calcium sulfoaluminate. The formation of this mineral phase further fills the microcracks inside the material. The presence of the calcium sulfate phase makes the hydration product more evenly distributed, while improving the toughness of the material and reducing the initiation and expansion of cracks.

[0013] In the system, the dissolution of slag and fly ash will release calcium ions, which will combine with phosphate ions in sodium phosphate to form insoluble calcium phosphate salts or other calcium-related phosphate compounds. The formation of calcium phosphate salts will reduce the concentration of calcium ions in the solution, break the balance of the calcium silicate phase of slag, and further promote the dissolution of slag. The amorphous silicon-aluminum (Si-Al) components in fly ash are also more easily dissolved under the condition of reduced calcium ion concentration. Calcium phosphate salts are distributed in the slurry in the form of fine particles, filling the pore structure, reducing the porosity of the hardened slurry, and improving the density and compressive strength of the material. At the same time, sodium phosphate affects the curing process of the geopolymer system by generating calcium-phosphorus compounds. After the calcium ion concentration is reduced, the dissolution rate of slag is accelerated, more silicon-aluminum species are released, and gel is quickly generated, thereby accelerating the coagulation of the system. Calcium phosphate salts are quickly precipitated in the early stage to form a solid phase. This solid phase not only plays a filling role, but also further promotes the formation of calcium aluminum silicate hydrate and sodium aluminum silicate hydrate gel. In the geopolymer system, the alkaline activator promotes the dissolution of fly ash and slag. However, too high alkalinity may lead to too fast a reaction rate, causing the slurry to quickly lose fluidity, affecting construction operability, or causing excessive heat release. Too strong alkaline reaction will cause the system to release a lot of heat, which may cause cracks or expansion. Sodium phosphate has a certain buffering capacity. In a high alkaline environment, phosphate ions can react with OH - Reaction, reducing free OH - The concentration is adjusted to avoid the reaction from being out of control too quickly, prolonging the operability time of the slurry. In addition, the fine calcium phosphate particles generated by sodium phosphate provide more nucleation points for the gelation reaction, making the formation of calcium aluminum silicate hydrate and sodium aluminum silicate hydrate in the system more uniform.

[0014] The amorphous silica and alumina in fly ash and slag powder are amorphous, have certain chemical inertness and poor solubility at room temperature. At high temperatures of 450-500°C, the heat input causes the chemical bonds in the amorphous materials to break locally, generating more active sites. Slag powder is rich in calcium-based components, mainly in the form of amorphous calcium silicates, which easily release soluble calcium ions under high temperature conditions. Sodium sulfate and sodium phosphate dissociate at high temperatures, releasing SO 4 2- and PO 4 3- ions. These anions react with the Ca 2+ and Al 2 O 3 The reaction occurs to generate calcium sulfate and calcium aluminum silicate phases. The presence of calcium sulfate promotes the continuous release of calcium ions in the slag powder. 2 O 3 and SiO 2 With Ca2+ and SO 4 2- The combined effects generate calcium aluminum silicate composite phases, which are highly reactive and can further dissolve and participate in the formation of gel in the subsequent hydration process. At the same time, high temperature treatment not only stimulates the activity of the raw materials, but may also directly generate precursors of some hydration products, such as microcrystalline CSH and CASH. These microcrystalline precursors can be further dissolved and reorganized in the subsequent alkali excitation process to generate a denser and more stable gel network. The presence of hydration product precursors accelerates the early reaction rate and improves the early strength of the material.

[0015] Polyethylene glycol is a hydrophilic polymer with rich hydrogen bond donors in its molecular structure. It can lubricate and modify the particle surface through weak physical adsorption or chemical bonding, thereby reducing the interaction between particles, preventing particle agglomeration, and forming a molecular-scale lubricating layer in the slurry, thereby improving the fluidity and dispersibility of the particles. The groups of silane coupling agents are hydrolyzed in water and alkaline environments to generate silanols. In acidic environments, silanols undergo polycondensation reactions to generate silicon-oxygen bonds and form a network structure. Polyethylene glycol molecules are adsorbed on the surface of particles to form a hydrophilic lubricating film, which reduces the cohesion between particles. The silanol generated by the hydrolysis of silane can chemically adsorb with the hydroxyl groups or other active groups (Al-OH, Si-OH) on the surface of particles to form chemical crosslinks. The silicon-oxygen bonds generated by the silane polycondensation further stabilize the modified layer on the surface of the particles, improving its hydrophilicity and dispersibility. The synergistic effect of polyethylene glycol and silane coupling agent forms a composite layer with lubricating and hydrophilic properties on the surface of the particles, improving the surface properties of the particles. The optimized particle dispersibility and lubrication effect enable the slurry to flow under lower shear force, thereby improving the fluidity of the geopolymer grouting material.

[0016] 1-Ethyl-3-methylimidazolium tetrafluoroborate solution has high polarity and ionic conductivity, and can provide good ion shielding effect for particles in the system. After the dissociation of 1-ethyl-3-methylimidazolium tetrafluoroborate, its cations and anions can be adsorbed on the surface of aluminosilicate particles to form an electrostatic shielding layer, reducing the electrostatic attraction between particles. This ion shielding effect reduces the tendency of particles to agglomerate, thereby achieving a more uniform dispersion. The high polarity of ionic liquids enables them to destroy the stability of Si-O and Al-O bonds in the aluminosilicate network. Anions coordinate with cations in aluminosilicates to promote the dissolution of amorphous aluminosilicate components in the system. Cations further enhance the polarity of the dissolution environment by interacting with water molecules or hydroxyls in the solution. Ionic liquids significantly reduce the internal friction of the slurry by improving the dispersibility and fluidity of particles and reducing the interaction between particles, thereby reducing viscosity. Amide-based polymer is a multifunctional polymer material containing functional groups such as amide, carboxyl and sulfonic acid. The amide has a polar structure, in which the lone pair of electrons on the nitrogen atom and the hydrogen atom in the amide can form hydrogen bonds with the hydroxyl groups on the surface of the particles respectively. The amide is firmly adsorbed on the surface of the particles through hydrogen bonds and forms a stable molecular layer. This adsorption effectively covers the active sites on the surface of the particles, reduces the direct contact and agglomeration tendency between particles, and the amide forms a "protective layer" on the surface of the particles. This protective layer has physical and chemical stability, can inhibit the agglomeration behavior of the particles, and enhance the dispersibility of the particles. The carboxyl group is partially ionized into carboxylate in the alkaline environment of the slurry, which carries a negative charge. The sulfonic acid group is a strong acidic group, which is completely ionized into sulfonate in the slurry. The negative charges carried by the carboxylate and sulfonate groups can be adsorbed on the particle surface through electrostatic action, making the particle surface negatively charged. The negative charges on the particle surface repel each other, reducing the attraction between the particles, thereby enhancing the dispersibility of the particles. The sulfonic acid group has a strong adsorption capacity. Compared with the carboxylate, its chemical adsorption on the particle surface is more solid. The strong adsorption of the sulfonic acid group not only further increases the negative charge of the particle surface, but also enhances the stable dispersion state of the particles. After the amide polymer is adsorbed on the particle surface, its long chain structure forms an adsorption layer of uniform thickness around the particle. The polymer chain covers the particle surface through physical adsorption (such as hydrogen bonding) and chemical bonding (such as electrostatic adsorption). These polymer chains provide a physical barrier between the particles to prevent direct contact between the particles. The adsorption layer formed by the polymer chain on the particle surface forms a "steric hindrance" around the particle due to the flexibility of the molecular chain. When particles approach, the repulsive force between the adsorption layers prevents the particles from getting closer, thus effectively inhibiting agglomeration behavior. The steric hindrance effect combined with the electrostatic repulsion effect keeps the particles in a good dispersion state in the slurry and prevents the particles from settling or agglomerating. The weak chemical bonding of the amide and carboxyl groups stabilizes the aluminosilicate species, reduces its migration energy barrier, and makes it easier to participate in the polycondensation reaction of the geopolymer.This chemical bonding promotes the rapid formation of the gel phase, thereby improving the early strength of the material.

[0017] The synergistic effect of ionic liquids and amide-based polymers is manifested in the slurry system as follows: ionic liquids improve the dispersibility of particles through ion shielding effect, while amide-based polymers further stabilize the dispersion state of particles. Ionic liquids reduce the electrostatic attraction between particles, and amide-based polymers prevent secondary aggregation of particles through molecular adsorption and steric hindrance effect. The polar environment of ionic liquids reduces the friction on the surface of particles, while the lubricating layer of amide-based polymers further reduces the mechanical resistance between particles. This dual lubrication effect significantly reduces the viscosity of the slurry and improves fluidity. Ionic liquids enhance the solubility of aluminosilicates, while amide-based polymers promote the condensation reaction of reactants through weak chemical bonding with dissolved species. Ionic liquids provide an efficient dissolution environment, and amide-based polymers stabilize dissolved aluminosilicate species and promote their further polymerization into a gel phase. The ionic liquids and amide-based polymers work together to improve the dynamic rheological properties of the slurry. Under shear, ionic liquids provide rapid particle dispersion adjustment capabilities, giving the slurry excellent shear-thinning properties. The amide-based polymer provides a certain elasticity and cohesion to the slurry through the flexible behavior of the molecular chain, preventing the slurry from stratification or segregation; the synergistic effect of the ionic liquid and the amide-based polymer accelerates the alkali-induced reaction, generating more calcium aluminum silicate hydrate and sodium aluminum silicate hydrate gel phases, thereby improving the early strength of the material.

[0018] As a preferred technical solution of the present invention, in step A1, the mass ratio of the fly ash to the granulated blast furnace slag powder is 5:7.

[0019] In some optional examples, the mass ratio of the fly ash, sodium sulfate and sodium phosphate is 50:3:2.

[0020] In some optional instances, the first temperature is 450-500°C, for example, 450.0°C, 455.0°C, 460.0°C, 465.0°C, 470.0°C, 475.0°C, 480.0°C, 485.0°C, 490.0°C, 495.0°C or 500.0°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0021] In some optional examples, the insulation time is 2-3h, for example, it can be 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0022] As a preferred technical solution of the present invention, in step A2, in the polyethylene glycol aqueous solution, the mass ratio of polyethylene glycol to deionized water is 1:150, and the polyethylene glycol is polyethylene glycol-400.

[0023] In some optional examples, the mass volume ratio of the polyethylene glycol to triethylamine is 2g:1mL.

[0024] In some optional examples, the silane mixture is polydimethylsiloxane and tetraethoxysilane in a volume ratio of 4:1.

[0025] In some optional examples, the volume ratio of triethylamine to polydimethylsiloxane is 1:40.

[0026] In some optional examples, the silane coupling agent mixture is KH-560 and KH-550, and the volume ratio is 3:2.

[0027] In some optional examples, in the ethanol aqueous solution, the volume ratio of anhydrous ethanol to deionized water is 10:1.

[0028] In some optional examples, the volume ratio of the silane coupling agent mixed liquid to anhydrous ethanol is 1:1.

[0029] In some optional examples, the mass volume ratio of the lubricating precursor and the silane coupling agent mixed liquid is 1g:1mL.

[0030] In some optional instances, the second temperature is 60-70°C, for example, it can be 60.0°C, 61.0°C, 62.0°C, 63.0°C, 64.0°C, 65.0°C, 66.0°C, 67.0°C, 68.0°C, 69.0°C or 70.0°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] In some optional examples, the reaction time at the second temperature is 6-7h, for example, it can be 6.0h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h or 7.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0032] In some optional examples, the mass ratio of the lubricating particles to deionized water is 1:10.

[0033] As a preferred technical solution of the present invention, in step A3, the mass ratio of N-vinylformamide, 2-acrylamido-2-methylpropanesulfonic acid, methacrylic acid and dodecyl methacrylate is 5:4:0.4:1.3;

[0034] In some optional examples, the mass ratio of the deionized water to N-vinylformamide is 60:1.

[0035] In some optional instances, the third temperature is 55-60°C, for example, it can be 55.0°C, 55.5°C, 56.0°C, 56.5°C, 57.0°C, 57.5°C, 58.0°C, 58.5°C, 59.0°C, 59.5°C or 60.0°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] In some optional examples, the initiator is potassium persulfate and sodium sulfite in a mass ratio of 5:2.

[0037] In some optional examples, the mass ratio of N-vinylformamide to initiator is 5:0.7.

[0038] In some optional examples, the stirring reaction time is 4-5h, for example, it can be 4.0h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5.0h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0039] In some optional examples, the mass fraction of the 1-ethyl-3-methylimidazolium tetrafluoroborate solution is 4 wt.%.

[0040] In some optional examples, the mass fraction of the product A solution is 0.5 wt.%.

[0041] In some optional examples, the mass ratio of the 1-ethyl-3-methylimidazolium tetrafluoroborate solution to the product A solution is 4:1.

[0042] As a preferred technical solution of the present invention, in step S1, the mass ratio of water glass to sodium hydroxide is (30-45): (3-5).

[0043] In some optional examples, the mass ratio of the fly ash, granulated blast furnace slag powder and the pre-reaction active phase is 40:50:10.

[0044] In some optional examples, the mass ratio of water glass to fly ash+granulated blast furnace slag powder+pre-reaction active phase is (30-45):100.

[0045] In some optional examples, the fly ash technical requirements are: density ≤2.6g / cm3, loss on ignition ≤8%, fineness (45 square hole sieve) residue ≤30%, strength activity index ≥70.0%, total mass fraction of silicon dioxide, aluminum oxide and iron oxide ≥70.0%, mass fraction of free calcium oxide ≤1.0%, and mass fraction of sulfur trioxide ≤3.5%.

[0046] In some optional examples, the granulated blast furnace slag powder has the following technical requirements: specific surface area ≥ 400m 2 / kg, loss on ignition ≤1.0%, density ≥2.8g / cm 3 , strength activity index (28d) ≥ 95.0%, mass fraction of sulfur trioxide ≤ 4.0%.

[0047] In some optional examples, the water glass technical requirement is: the water glass modulus is 3.0-3.2.

[0048] As a preferred technical solution of the present invention, in step S2, the mass ratio of water, lubricating dispersion, rheological agent, water reducing agent, swelling agent, sodium citrate, sodium sulfate, sodium phosphate, sodium ethylenediaminetetraacetic acid, dispersible rubber powder and defoaming agent is (25-40): (3-5): (3-5): (1-2): (2-6): (1-2): (3-5): (2-4): (0.5-1): (0.1-1.5): (0.1-1).

[0049] As a preferred technical solution of the present invention, in step S3, the first stirring speed is 400-800rpm, for example, it can be 450rpm, 500rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm or 800rpm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0050] In some optional examples, the mass ratio of the fiber to fly ash+granulated blast furnace slag powder+pre-reaction active phase is (0.1-0.3):100.

[0051] In some optional examples, the mass ratio of the sand to the fly ash+granulated blast furnace slag powder+pre-reaction active phase is (10-15):100.

[0052] In some optional examples, the second stirring speed is 1600-2400rpm, for example, it can be 1600rpm, 1700rpm, 1800rpm, 1900rpm, 2000rpm, 2100rpm, 2200rpm, 2300rpm or 2400rpm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0053] In some optional examples, the sand technical requirements are: 100% pass rate of 1.18mm square hole sieve, ≥95% pass rate of 0.6mm, and ≤2% pass rate of 0.075mm square hole sieve. It can be natural sand, machine-made sand, or a mixture of the two.

[0054] In a second aspect, the present invention provides an early-strength high-fluidity geopolymer grouting material prepared by the preparation method described in the first aspect.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] (1) The present invention uses 1-ethyl-3-methylimidazolium tetrafluoroborate to dissolve and activate the aluminosilicate component. The ionic liquid significantly improves the solubility of the aluminosilicate-based components (such as fly ash and slag powder) through its high polarity and ionic conductivity. The anions destroy the silicon-oxygen and aluminum-oxygen bonds through coordination with the metal ions in the aluminosilicate. The cations further enhance the dissolution environment by forming hydrogen bonds with water molecules or hydroxyl groups, thereby providing more reaction species for the subsequent polycondensation reaction.

[0057] (2) The present invention introduces a functionalized amide polymer, which physically adsorbs and chemically bonds with the particle surface through its functional groups (amide, sulfonic acid, carboxyl). The amide group interacts with the hydroxyl groups (such as Si-OH or Al-OH) on the particle surface through hydrogen bonds to form a stable adsorption layer. The carboxyl and sulfonic acid groups are partially ionized in an alkaline environment to generate negative charges, which further enhance the dispersibility of the particles through the electrostatic repulsion effect. The flexibility of the polymer chain forms a steric hindrance around the particles, further inhibiting the agglomeration behavior of the particles. The ionic liquid in the slurry weakens the electrostatic attraction between the particles through the ion shielding effect, while providing a uniform dispersion environment. The synergistic effect of the ionic liquid and the amide polymer further stabilizes the dispersion state of the particles.

[0058] (3) After the amide polymer is adsorbed on the surface of the particles, its flexible molecular chain reduces the mechanical friction between the particles in the slurry and reduces the viscosity of the slurry. The ionic liquid further reduces the internal friction of the slurry by improving the fluidity of the particle interface, making the slurry exhibit good shear thinning properties. The hydrophilic groups of the amide polymer (such as amide and carboxyl) form hydrogen bonds with water molecules, capturing free water in the slurry and enhancing the overall water retention performance of the slurry. The low volatility of the ionic liquid further delays the evaporation of water in the slurry.

[0059] (4) The amide and carboxyl groups can form weak chemical bonds with the soluble silicon and aluminum species in the slurry, promoting the rapid formation of calcium aluminum silicate hydrate and sodium aluminum silicate hydrate gel phases. The sulfonic acid group accelerates the migration rate of the reactants by improving the ionic conductivity of the slurry, making the reaction more uniform and rapid. The ionic liquid provides a more uniform chemical environment for the polycondensation reaction by enhancing its solubility and promoting ion diffusion. The synergistic effect of the amide polymer and the ionic liquid improves the chemical reactivity of the material system, accelerates the formation of the gel phase, and improves the early strength. DETAILED DESCRIPTION

[0060] The technical solution of the present invention is described in detail below in conjunction with specific embodiments. The embodiments recorded herein are specific embodiments of the present invention, which are used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary and should not be construed as limitations on the embodiments of the present invention and the scope of protection of the present invention. In addition to the embodiments recorded herein, those skilled in the art can also adopt other obvious technical solutions based on the contents disclosed in the claims of this application and its specification, including technical solutions that adopt any obvious replacements and modifications to the embodiments recorded herein.

[0061] The chemical reagents used in the examples and comparative examples of the present invention are all commercially available products without any further purification treatment.

[0062] Example 1

[0063] This embodiment provides a method for preparing an early-strength high-fluidity geopolymer grouting material, and the preparation method specifically comprises the following steps:

[0064] Step A1, 200 g of fly ash and 280 g of granulated blast furnace slag powder are mixed, and then 12 g of sodium sulfate and 8 g of sodium phosphate are added to prepare a dry powder mixture, and the mixture is heated to 470° C. and kept warm for 2.4 hours to obtain a pre-reaction active phase;

[0065] Step A2, in 302g of polyethylene glycol aqueous solution, add 1mL of triethylamine and then add 40mL of silane mixed solution, adjust the pH to 9, and obtain a lubricating precursor, add 5mL of silane coupling agent mixed solution to 55mL of ethanol aqueous solution, adjust the pH to 4, and then add 5g of lubricating precursor to the ethanol aqueous solution, heat to 62°C and react for 6.4h, and obtain lubricating particles after the reaction is completed, and then add 10g of lubricating particles to 100g of deionized water to obtain a lubricating particle dispersion;

[0066] Step A3, add 5g N-vinylformamide, 4g 2-acrylamido-2-methylpropanesulfonic acid, 0.4g methacrylic acid and 1.3g dodecyl methacrylate to 300mL deionized water in sequence, adjust the pH to 8, heat to 58°C, add 0.5g potassium persulfate and 0.2g sodium sulfite under nitrogen atmosphere, and stir to react for 4.3h. After the reaction, pour the polymer dispersion into anhydrous ethanol to precipitate the polymer, wash and freeze-dry to obtain product A, mix 40g of 4wt.% 1-ethyl-3-methylimidazolium tetrafluoroborate solution with 10g of 0.5wt.% product A solution to obtain a rheological agent;

[0067] Step S1, 990g of water glass and 96g of sodium hydroxide are mixed to obtain an alkali activator A, and 1200g of fly ash, 1500g of granulated blast furnace slag powder and 300g of pre-reaction active phase are mixed to obtain a powder;

[0068] Step S2, 870g of water, 105g of lubricating dispersion, 126g of rheological agent, 39g of water reducing agent, 75g of swelling agent, 36g of sodium citrate, 96g of sodium sulfate, 66g of sodium phosphate, 17.1g of sodium ethylenediaminetetraacetate, 4.2g of dispersible rubber powder, and 6.6g of defoaming agent are mixed and dispersed to obtain a mixed solution, and an alkali activator A is mixed with the mixed solution to obtain an alkali activator B, and 300g of natural sand and 6g of 6mm long polypropylene fiber are weighed for standby use;

[0069] Step S3, adding alkali activator B to the powder for an average of 3 times within 2n time, then stirring at the first stirring speed for n time, then adding sand and fiber and stirring at the first stirring speed for n time, then stirring at the second stirring speed for n time, stopping for 2n time after stirring evenly, and then stirring at the second stirring speed for 3n time to obtain an early-strength high-fluidity geopolymer grouting material.

[0070] Exemplarily, alkali activator B is added to the powder an average of 3 times within 60 seconds, then stirred at 600 rpm for 30 seconds, sand and fiber are added and stirred at 600 rpm for 30 seconds, then stirred at a second stirring speed of 1900 rpm for 30 seconds, stopped for 60 seconds after stirring evenly, and then stirred at 1900 rpm for 90 seconds to obtain an early-strength high-fluidity geopolymer grouting material.

[0071] Example 2

[0072] This embodiment provides a method for preparing an early-strength high-fluidity geopolymer grouting material, and the preparation method specifically comprises the following steps:

[0073] Step A1, 200 g of fly ash and 280 g of granulated blast furnace slag powder are mixed, and then 12 g of sodium sulfate and 8 g of sodium phosphate are added to prepare a dry powder mixture, and the mixture is heated to 450° C. and kept warm for 2.0 h to obtain a pre-reaction active phase;

[0074] Step A2, add 1 mL of triethylamine to 302 g of polyethylene glycol aqueous solution and then add 40 mL of silane mixed solution, adjust the pH to 9 to obtain a lubricating precursor, add 8 mL of the silane coupling agent mixed solution to 88 mL of ethanol aqueous solution, adjust the pH to 4, then add 8 g of the lubricating precursor to the ethanol aqueous solution, heat to 66° C. and react for 6.8 hours. After the reaction is completed, lubricating particles are obtained, and then 12 g of the lubricating particles are added to 120 g of deionized water to obtain a lubricating particle dispersion;

[0075] Step A3, add 5g N-vinylformamide, 4g 2-acrylamido-2-methylpropanesulfonic acid, 0.4g methacrylic acid and 1.3g dodecyl methacrylate to 300mL deionized water in sequence, adjust the pH to 8, heat to 55°C, add 0.5g potassium persulfate and 0.2g sodium sulfite under nitrogen atmosphere, and stir to react for 4.8h. After the reaction, pour the polymer dispersion into anhydrous ethanol to precipitate the polymer, wash and freeze-dry to obtain product A, mix 40g of 4wt.% 1-ethyl-3-methylimidazolium tetrafluoroborate solution with 10g of 0.5wt.% product A solution to obtain a rheological agent;

[0076] Step S1, mixing 1200 g of water glass and 114 g of sodium hydroxide to obtain an alkali activator A, and mixing 1200 g of fly ash, 1500 g of granulated blast furnace slag powder and 300 g of pre-reaction active phase to obtain a powder;

[0077] Step S2, 1140g of water, 111g of lubricating dispersion, 126g of rheological agent, 51g of water reducing agent, 141g of swelling agent, 51g of sodium citrate, 90g of sodium sulfate, 87g of sodium phosphate, 18.9g of sodium ethylenediaminetetraacetate, 11.4g of dispersible rubber powder, and 18.9g of defoaming agent are mixed and dispersed to obtain a mixed solution, and an alkali activator A is mixed with the mixed solution to obtain an alkali activator B, and 450g of natural sand and 4.5g of 6mm long polypropylene fiber are weighed for standby use;

[0078] Step S3, adding alkali activator B to the powder for an average of 3 times within 2n time, then stirring at the first stirring speed for n time, then adding sand and fiber and stirring at the first stirring speed for n time, then stirring at the second stirring speed for n time, stopping for 2n time after stirring evenly, and then stirring at the second stirring speed for 3n time to obtain an early-strength high-fluidity geopolymer grouting material.

[0079] Example 3

[0080] This embodiment provides a method for preparing an early-strength high-fluidity geopolymer grouting material, and the preparation method specifically comprises the following steps:

[0081] Step A1, 150 g of fly ash and 210 g of granulated blast furnace slag powder are mixed, and then 9 g of sodium sulfate and 6 g of sodium phosphate are added to prepare a dry powder mixture, and the mixture is heated to 500° C. and kept warm for 3.0 h to obtain a pre-reaction active phase;

[0082] Step A2, add 1 mL of triethylamine to 302 g of polyethylene glycol aqueous solution and then add 40 mL of silane mixed solution, adjust the pH to 9 to obtain a lubricating precursor, add 4 mL of the silane coupling agent mixed solution to 44 mL of ethanol aqueous solution, adjust the pH to 4, then add 4 g of the lubricating precursor to the ethanol aqueous solution, heat to 60° C. and react for 7.0 h. After the reaction, lubricating particles are obtained, and then 14 g of the lubricating particles are added to 140 g of deionized water to obtain a lubricating particle dispersion;

[0083] Step A3, add 5g N-vinylformamide, 4g 2-acrylamido-2-methylpropanesulfonic acid, 0.4g methacrylic acid and 1.3g dodecyl methacrylate to 300mL deionized water in sequence, adjust the pH to 8, heat to 60°C, add 0.5g potassium persulfate and 0.2g sodium sulfite under nitrogen atmosphere, and stir to react for 4.1h. After the reaction, pour the polymer dispersion into anhydrous ethanol to precipitate the polymer, wash and freeze-dry to obtain product A, mix 40g of 4wt.% 1-ethyl-3-methylimidazolium tetrafluoroborate solution with 10g of 0.5wt.% product A solution to obtain a rheological agent;

[0084] Step S1, 1350 g of water glass and 144 g of sodium hydroxide are mixed to obtain an alkali activator A, and 1200 g of fly ash, 1500 g of granulated blast furnace slag powder and 300 g of pre-reaction active phase are mixed to obtain a powder;

[0085] Step S2, 990g water, 138g lubricating dispersion, 150g rheological agent, 57g water reducing agent, 117g swelling agent, 52g sodium citrate, 126g sodium sulfate, 117g sodium phosphate, 29.1g sodium ethylenediaminetetraacetic acid, 24.9g dispersible rubber powder, and 14.4g defoaming agent are mixed and dispersed to obtain a mixed solution, and the alkaline activator A is mixed with the mixed solution to obtain an alkaline activator B; 300g machine-made sand and 6g 6mm long polypropylene fiber are weighed and set aside;

[0086] Step S3, adding alkali activator B to the powder for an average of 3 times within 2n time, then stirring at the first stirring speed for n time, then adding sand and fiber and stirring at the first stirring speed for n time, then stirring at the second stirring speed for n time, stopping for 2n time after stirring evenly, and then stirring at the second stirring speed for 3n time to obtain an early-strength high-fluidity geopolymer grouting material.

[0087] Example 4

[0088] This embodiment provides a method for preparing an early-strength high-fluidity geopolymer grouting material, and the preparation method specifically comprises the following steps:

[0089] Step A1, 200 g of fly ash and 280 g of granulated blast furnace slag powder are mixed, and then 12 g of sodium sulfate and 8 g of sodium phosphate are added to prepare a dry powder mixture, and the mixture is heated to 480° C. and kept warm for 2.8 hours to obtain a pre-reaction active phase;

[0090] Step A2, add 1 mL of triethylamine and then 40 mL of silane mixed solution to 302 g of polyethylene glycol aqueous solution, adjust the pH to 9 to obtain a lubricating precursor, add 6 mL of the silane coupling agent mixed solution to 66 mL of ethanol aqueous solution, adjust the pH to 4, then add 6 g of the lubricating precursor to the ethanol aqueous solution, heat to 70° C. and react for 6.1 h. After the reaction, lubricating particles are obtained, and then 13 g of the lubricating particles are added to 130 g of deionized water to obtain a lubricating particle dispersion;

[0091] Step A3, add 5g N-vinylformamide, 4g 2-acrylamido-2-methylpropanesulfonic acid, 0.4g methacrylic acid and 1.3g dodecyl methacrylate to 300mL deionized water in sequence, adjust the pH to 8, heat to 57°C, add 0.5g potassium persulfate and 0.2g sodium sulfite under nitrogen atmosphere, and stir to react for 5.0h. After the reaction, pour the polymer dispersion into anhydrous ethanol to precipitate the polymer, wash and freeze-dry to obtain product A, mix 40g of 4wt.% 1-ethyl-3-methylimidazolium tetrafluoroborate solution with 10g of 0.5wt.% product A solution to obtain a rheological agent;

[0092] Step S1, 1140 g of water glass and 126 g of sodium hydroxide are mixed to obtain an alkali activator A, and 1200 g of fly ash, 1500 g of granulated blast furnace slag powder and 300 g of pre-reaction active phase are mixed to obtain a powder;

[0093] Step S2, 750g of water, 144g of lubricating dispersion, 102g of rheological agent, 33g of water reducing agent, 162g of swelling agent, 60g of sodium citrate, 147g of sodium sulfate, 93g of sodium phosphate, 24.6g of sodium ethylenediaminetetraacetate, 41.4g of dispersible rubber powder, and 26.7g of defoaming agent are mixed and dispersed to obtain a mixed solution, and the alkaline activator A is mixed with the mixed solution to obtain an alkaline activator B; 200g of natural sand, 150g of machine-made sand, and 5.0g of 3mm long polypropylene fiber are weighed for use;

[0094] Step S3, adding alkali activator B to the powder for an average of 3 times within 2n time, then stirring at the first stirring speed for n time, then adding sand and fiber and stirring at the first stirring speed for n time, then stirring at the second stirring speed for n time, stopping for 2n time after stirring evenly, and then stirring at the second stirring speed for 3n time to obtain an early-strength high-fluidity geopolymer grouting material.

[0095] Comparative Example 1

[0096] This comparative example provides a method for preparing an early-strength high-fluidity geopolymer grouting material, which differs from Example 1 in that in step A2, the volume of the silane coupling agent mixture is 12 mL, which is 6 mL more than that in Example 1, and the other process parameters and operating conditions are exactly the same as those in Example 1.

[0097] Comparative Example 2

[0098] This comparative example provides a method for preparing an early-strength high-fluidity geopolymer grouting material, which differs from Example 1 in that in step A2, the volume of the silane coupling agent mixture is 1 mL, which is 5 mL less than that in Example 1, and the other process parameters and operating conditions are exactly the same as those in Example 1.

[0099] Comparative Example 3

[0100] This comparative example provides a method for preparing an early-strength high-fluidity geopolymer grouting material, which differs from Example 1 in that in step A3, the mass of N-vinylformamide is 10 g, which is 5 g more than that in Example 1, and the other process parameters and operating conditions are exactly the same as those in Example 1.

[0101] Comparative Example 4

[0102] This comparative example provides a method for preparing an early-strength high-fluidity geopolymer grouting material, which differs from Example 1 in that in step A3, the mass of N-vinylformamide is 1 g, which is 4 g less than that in Example 1, and the other process parameters and operating conditions are exactly the same as those in Example 1.

[0103] The test standard of the geopolymer grouting material prepared in the present invention is JG / T408-2013, and the test results of the geopolymer grouting material prepared in the present invention are shown in Table 1.

[0104] Table 1 Test results of early strength high fluidity geopolymer grouting materials prepared in Examples 1-4 and Comparative Examples 1-4

[0105]

[0106] It can be seen from Table 1 that, compared with Example 1, the compressive strength and fluidity of Comparative Example 1 are lower than those of Example 1, and the vertical expansion rate, coagulation time and water bleeding rate are higher than those of Example 1; the compressive strength and fluidity of Comparative Example 2 are lower than those of Example 1, and the vertical expansion rate, coagulation time and water bleeding rate are higher than those of Example 1. The silane coupling agent mixture contains epoxy groups and amino functional groups, which can form chemical bonds with hydroxyl groups on the surface of inorganic substrates. At the same time, the amino groups can react ionically with acidic groups (such as sodium sulfate or sodium phosphate in the slurry) to enhance the interface interaction, and improve the lubricity, dispersibility and stability of the particle interface by forming a chemical modification layer on the particle surface, while regulating the chemical interaction between particles to affect the microstructure and overall performance of the slurry. In comparative example 1, the silane coupling agent mixture is excessive, and a thick organic modification layer may be formed on the surface of the particles, which hinders the effective contact between the particles and the alkali excitation reaction, resulting in a decrease in the rate of formation of the gel phase. In addition, the organic part of the coupling agent may introduce too many unreacted organic functional groups in the early reaction, reducing the compressive strength and fluidity, and too much silane coupling agent is unreacted, affecting the stability of the slurry. In comparative example 2, the silane coupling agent mixture is too little, and the lubrication modification layer on the surface of the particles is not complete, resulting in increased direct contact and agglomeration between the particles. The agglomerated particles will form an uneven gel phase in the alkali excitation reaction. At the same time, the lubrication between the particles is insufficient, the particles are easy to agglomerate, the internal friction of the slurry increases, and the fluidity decreases. Insufficient lubricity of the particles will lead to a decrease in the fluidity of the slurry, and the particles cannot be evenly distributed. The slurry may shrink locally or expand unevenly during the coagulation and hardening process.

[0107] It can be seen from Table 1 that, compared with Example 1, the compressive strength and fluidity of Comparative Example 3 are lower than those of Example 1, the vertical expansion rate and coagulation time are higher than those of Example 1, and the water bleeding rate remains unchanged; the compressive strength and fluidity of Comparative Example 4 are lower than those of Example 1, and the vertical expansion rate, coagulation time and water bleeding rate are higher than those of Example 1. This is because, in Comparative Example 3, when the amount of N-vinylformamide is too much, the generated polymer contains too many amide groups, and excessive cross-linking may occur between polymer chains, resulting in decreased fluidity of the slurry, easy agglomeration between particles, resulting in low efficiency of gel phase generation, and prolonged coagulation time. When N-vinylformamide is excessive, the polymer may absorb too much free water, keeping the water bleeding rate unchanged. In Comparative Example 4, when the dosage of N-vinylformamide is insufficient, the number of amide groups formed in the polymer is small, and the adsorption and functional modification effects on the particle surface are not significant, resulting in weak interfacial bonding between particles and reduced fluidity. During the alkali excitation process, the gel phase is unevenly distributed, resulting in reduced strength. When N-vinylformamide is insufficient, the lubrication and dispersion effects between particles are poor, the alkali excitation reaction rate is reduced, the formation of the gel phase is inhibited, and the coagulation time of the slurry is prolonged.

[0108] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention are within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing an early-strength high-fluidity geopolymer grouting material, characterized in that: The preparation method is: Step S1, mixing water glass and sodium hydroxide to obtain an alkali activator A, and mixing fly ash, granulated blast furnace slag powder and a pre-reaction active phase to obtain a powder; Step S2, mixing and dispersing water, lubricating particle dispersion, rheological agent, water reducing agent, swelling agent, sodium citrate, sodium sulfate, sodium phosphate, sodium ethylenediaminetetraacetate, dispersible rubber powder, and defoaming agent to obtain a mixed solution, and mixing alkaline activator A with the mixed solution to obtain alkaline activator B; Step S3, adding alkali activator B to powder material for an average of 3 times within 2n time, then stirring at a first stirring speed for n time, then adding sand and fiber and stirring at the first stirring speed for n time, then stirring at a second stirring speed for n time, stopping for 2n time after stirring evenly, and then stirring at the second stirring speed for 3n time to obtain an early strength high fluidity geopolymer grouting material; Step A1, mixing fly ash and granulated blast furnace slag powder, and then adding sodium sulfate and sodium phosphate to prepare a dry powder mixture, and heating and keeping the mixture warm to obtain a pre-reaction active phase; Step A2, adding triethylamine and then a silane mixture to a polyethylene glycol aqueous solution, adjusting the pH to 9 to obtain a lubricating precursor, adding the silane coupling agent mixture to an ethanol aqueous solution, adjusting the pH to 4, and then adding the lubricating precursor to the ethanol aqueous solution, heating the reaction to obtain lubricating particles, and then adding the lubricating particles to deionized water to obtain a lubricating particle dispersion; Step A3, add N-vinylformamide, 2-acrylamido-2-methylpropanesulfonic acid, methacrylic acid and dodecyl methacrylate to deionized water in sequence, adjust the pH to 8, heat, add an initiator under a nitrogen atmosphere, and obtain product A after the reaction is completed. Mix 1-ethyl-3-methylimidazolium tetrafluoroborate solution with the product A solution to obtain a rheological agent.

2. The method for preparing an early-strength high-fluidity geopolymer grouting material according to claim 1, characterized in that: In step S1, The mass ratio of water glass to sodium hydroxide is (30-45): (3-5); The mass ratio of the fly ash, granulated blast furnace slag powder and pre-reaction active phase is 40:50:10; The mass ratio of water glass to fly ash + granulated blast furnace slag powder + pre-reaction active phase is (30-45): 100; In step S2, The mass ratio of water, lubricating particle dispersion, rheological agent, water reducing agent, swelling agent, sodium citrate, sodium sulfate, sodium phosphate, sodium ethylenediaminetetraacetic acid, dispersible rubber powder and defoaming agent is (25-40): (3-5): (3-5): (1-2): (2-6): (1-2): (3-5): (2-4): (0.5-1): (0.1-1.5): (0.1-1); In step S3, The mass ratio of the fiber to fly ash+granulated blast furnace slag powder+pre-reaction active phase is (0.1-0.3): 100; The mass ratio of the sand to the fly ash+granulated blast furnace slag powder+pre-reaction active phase is (10-15):

100.

3. The method for preparing an early-strength high-fluidity geopolymer grouting material according to claim 1, characterized in that: The water reducer is one or more of a polycarboxylic acid high performance water reducer, a naphthalene high efficiency water reducer, and an amino high efficiency water reducer; The expansion agent is one or more of calcium sulphoaluminate, calcium oxide and magnesium oxide.

4. The method for preparing an early-strength high-fluidity geopolymer grouting material according to claim 1, characterized in that: In step A1, The mass ratio of the fly ash to the granulated blast furnace slag powder is 5:7; The mass ratio of the fly ash, sodium sulfate and sodium phosphate is 50:3:

2.

5. The method for preparing an early-strength high-fluidity geopolymer grouting material according to claim 1, characterized in that: In step A2, In the polyethylene glycol aqueous solution, the mass ratio of polyethylene glycol to deionized water is 1:150, and the polyethylene glycol is polyethylene glycol-400; The silane mixture is polydimethylsiloxane and tetraethoxysilane in a volume ratio of 4:1; The mass volume ratio of the lubricating precursor and the silane coupling agent mixed liquid is 1g:1mL; The mass ratio of the lubricating particles to deionized water is 1:

10.

6. The method for preparing an early-strength high-fluidity geopolymer grouting material according to claim 1, characterized in that: In step A3, The mass ratio of N-vinylformamide, 2-acrylamido-2-methylpropanesulfonic acid, methacrylic acid and dodecyl methacrylate is 5:4:0.4:1.3; The mass fraction of the 1-ethyl-3-methylimidazolium tetrafluoroborate solution is 4wt.%; The mass fraction of the product A solution is 0.5wt.%; The mass ratio of the 1-ethyl-3-methylimidazolium tetrafluoroborate solution to the product A solution is 4:

1.

7. An early-strength high-fluidity geopolymer grouting material obtained according to the preparation method according to any one of claims 1 to 6.

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