A highly permeable grouting material for treating seepage water diseases and a preparation method thereof

Abstract

The present invention discloses a highly permeable grouting material for treating seepage water diseases and a preparation method thereof, belonging to the technical field of energy-saving and environmental protection building materials. The material uses 525-type sulfoaluminate cement, fly ash, isophorone diisocyanate, polyvinyl acetate and a nano modifier as main raw materials. By optimizing the formulation ratio and preparation process, the fluidity, permeability and solidified body performance of the grouting material are significantly improved. The nano modifier enhances the compactness and interfacial bonding force of the slurry through efficient dispersion and cross-linking reactions, effectively reduces the porosity, and improves the anti-seepage performance and compressive strength. The preparation method includes steps such as raw material weighing and pretreatment, mixing reaction and temperature-controlled stirring to ensure the stability of the slurry performance and construction adaptability. The material of the present invention has low viscosity, high permeability, rapid curing, high strength and good environmental adaptability, and can be widely used in the treatment of seepage water in underground projects, with significant advantages such as convenient construction, environmental protection and economy.

Description

Technical Field

[0001] The present invention belongs to the technical field of energy-saving and environmental protection building materials. Specifically, it relates to a highly permeable grouting material for treating seepage and leakage diseases and a preparation method thereof. Background Technique

[0002] In underground engineering and tunnel construction, the problem of seepage and leakage has always been a major challenge in engineering construction and maintenance. Seepage and leakage not only affect the stability and durability of the engineering structure, but may also cause environmental problems such as pollution of underground water resources and ground settlement. Therefore, it is particularly important to develop and apply efficient seepage and leakage treatment materials and technologies.

[0003] Traditional seepage and leakage treatment methods mainly include mechanical plugging, chemical grouting, and physical plugging, etc. Mechanical plugging usually uses materials such as concrete and mortar for repair, but this method has poor effects when facing fine cracks or complex geological conditions. Chemical grouting injects chemical slurries into cracks or voids and uses the solidified bodies generated by their chemical reactions to block the leakage channels. Common chemical grouting materials include cement, water glass, polyurethane, acrylate, etc. However, these materials also have some limitations in practical applications: Cement-based slurries: Cement slurries have a relatively high viscosity, are difficult to penetrate into fine cracks, and are easily diluted by groundwater in highly permeable formations, resulting in poor reinforcement effects. In addition, the setting time of cement slurries is relatively long, and the construction efficiency is low.

[0004] Water glass slurries: Water glass (sodium silicate) slurries have good permeability, but the strength of the silicic acid gel formed after curing is relatively low, and it is easily washed away under high water pressure, resulting in an unpersistent water blocking effect.

[0005] Polyurethane slurries: Polyurethane materials have good elasticity and adhesiveness, can adapt to small deformations of the structure, and are suitable for plugging deformation joints and cracks. However, its cost is relatively high, and the reaction speed slows down in low-temperature environments, affecting the construction progress.

[0006] Acrylate slurries: Acrylate materials have attracted attention due to their low viscosity and high permeability, can penetrate into fine cracks, and form high-strength solidified bodies. However, the ratio and construction process of acrylate materials have a great influence on their performance and need to be precisely controlled.

[0007] With the continuous development of engineering construction, especially the construction of large-scale underground projects such as high-speed railways, subways, and underground utility tunnels, the requirements for seepage and leakage treatment materials are getting higher and higher. The research and application of highly permeable grouting materials have become the key to solving this problem. Highly permeable grouting materials need to have the following characteristics: Low viscosity: Ensure that the slurry can penetrate into fine cracks and pores.

[0008] High permeability: It can effectively diffuse in high-permeability formations and form a continuous solidified body.

[0009] Quick reaction: It can rapidly solidify during construction, reducing the construction time.

[0010] High strength: The solidified material has sufficient compressive and tensile strength to ensure long-term water-blocking effect.

[0011] Environmental friendliness: The material should be non-toxic and harmless, meeting environmental protection requirements.

[0012] Strong adaptability: It can adapt to different geological conditions and temperature changes.

[0013] Currently, there are already some high-permeability grouting materials on the market, but there are still some problems in their actual applications, such as: Complex material ratio: Precise control of the proportion of each component is required. A slight oversight may lead to a decline in material performance.

[0014] High requirements for construction technology: Professional construction teams and equipment are needed, and the construction difficulty is high.

[0015] Higher cost: The cost of high-performance materials is often high, increasing the economic burden of the project.

[0016] Environmental adaptability: The performance of some materials is unstable in low-temperature or high-temperature environments, affecting the construction effect.

[0017] Therefore, developing a grouting material that can not only meet the requirements of high permeability but also be easy to operate, have a moderate cost, be environmentally friendly and have good durability during construction has become a research hotspot in the field of underground engineering leakage treatment. The purpose of this invention is to provide a high-permeability grouting material and its preparation method for leakage disease treatment by optimizing the material formula and preparation process, so as to solve the above problems and improve the construction efficiency and quality of underground engineering. Summary of the Invention

[0018] Problems to be Solved

[0019] The leakage problems in underground engineering and tunnel construction have always been difficult problems in engineering construction and maintenance. Traditional leakage treatment methods (such as mechanical plugging, chemical grouting, etc.) have poor effects when facing fine cracks or complex geological conditions, and there are the following main problems: Cement-based slurries: High viscosity, poor permeability, difficult to fill small cracks, and easily diluted by groundwater.

[0020] Sodium silicate slurries: Low strength and the water-blocking effect is not lasting.

[0021] Polyurethane slurries: High cost and slow reaction speed in low-temperature environments.

[0022] Acrylate slurries: Their performance is greatly affected by the ratio and process, and precise control is required.

[0023] With the construction of large-scale underground projects (such as subways, high-speed railways, and underground utility tunnels), higher requirements are put forward for grouting materials, including low viscosity, high permeability, rapid curing, high strength, environmental protection, and strong adaptability.

[0024] Technical solution

[0025] To solve the above problems, the present invention adopts the following technical solution.

[0026] A highly permeable grouting material for treating seepage and leakage diseases, by weight, comprises the following raw materials: Type 525 sulfoaluminate cement: 64 parts - 90 parts, fly ash: 15 parts - 30 parts, isophorone diisocyanate: 4 parts - 8 parts, polyvinyl acetate: 10 parts - 20 parts, nano modifier: 8 parts - 20 parts.

[0027] Preferably, by weight, it comprises the following raw materials: Type 525 sulfoaluminate cement: 70 parts - 80 parts, fly ash: 18 parts - 25 parts, isophorone diisocyanate: 4 parts - 8 parts, polyvinyl acetate: 15 parts - 20 parts, nano modifier: 14 parts - 18 parts.

[0028] Preferably, by weight, it comprises the following raw materials: Type 525 sulfoaluminate cement: 75 parts, fly ash: 22 parts, isophorone diisocyanate: 6 parts, polyvinyl acetate: 18 parts, nano modifier: 16 parts.

[0029] Preferably, the parameters of the fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide. The density of the fly ash is 2.43 g / cm 3 . The fly ash particles are relatively fine, with uneven particle sizes, approximately between 200 - 400 μm.

[0030] Preferably, the cas number of the isophorone diisocyanate is 4098 - 71 - 9, and the relative density is 1.049; the cas number of the polyvinyl acetate is 9003 - 20 - 7, and the relative density is 1.18.

[0031] Preferably, the preparation method of the nano modifier is as follows: Heat the polyurethane emulsion to 40 - 50 °C and continuously stir to make it stably dispersed; Under the stirring state, slowly drop 0.1 - 0.3 times the weight of polyvinyl alcohol into the polyurethane emulsion. After the dropping is completed, add 0.1 times the weight of diammonium hydrogen citrate nanoparticles and 0.2 times the weight of sodium carboxyethylsilanetriol particles of the polyurethane emulsion, and continue to stir for 30 - 60 min to fully disperse the particles into the polyurethane emulsion; React at 80 - 90 °C for 30 - 60 min, slowly cool down to room temperature, and let it stand, and finally air-dry and dry it naturally.

[0032] The parameters of the polyurethane emulsion (PU-601) are as follows. Appearance: Milky white translucent liquid. Density: 1.3 g / cm 3 . Solids content: 60%. Viscosity: ≤60 s (PU-601). PH value: 8.0 ± 1 (PU-601). Particle size: 200 nm. Yellowing property: Grade four (PU-601). Elongation at break: ≈1000% (PU-601). Resilience: 100% (PU-601). Cold resistance: No bursting at -25 °C (PU-601). Film formation: Soft, transparent, and smooth to the touch (PU-601).

[0033] The CAS number of the diammonium hydrogen citrate nanoparticles is 3012-65-5, molecular weight is 226.19, appearance is white granular, with an ammonia smell, density is 1.48 g / mL, melting point is 185 °C, water solubility is soluble in water, slightly soluble in ethanol, and the acid-base property is that the aqueous solution is weakly acidic.

[0034] The CAS number of the sodium carboxyethylsilanetriol particles is 18191-40-7, molecular weight is 174.16, appearance is white particles, density is 1.17 g / mL, and water solubility is to form a stable aqueous solution.

[0035] The preparation method of the highly permeable grouting material for treating seepage water diseases includes the following steps: Raw material weighing and pretreatment: Accurately weigh the raw materials according to parts by weight to ensure that all powder raw materials are dry and free of lumps; If there is agglomeration or the particle size does not meet the requirements, perform sieving or grinding treatment.

[0036] Mixing and reaction: Place the weighed 525-type sulfoaluminate cement, fly ash, and nano modifier in a mixer, then add 20 times the weight of water of the 525-type sulfoaluminate cement, and then slowly add polyvinyl acetate under stirring conditions to initially disperse and form a dispersion liquid. Continue to stir for 3 - 5 min, control the temperature not to exceed 40 °C, and then slowly drop isophorone diisocyanate into the above dispersion liquid according to the formula dosage, and continue to stir for 5 - 10 min, control the temperature to be 25 - 35 °C to obtain a slurry, and then filter the slurry with a filter screen or filter bag for later use.

[0037] Beneficial effects

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows: The introduction of the nano modifier significantly improves the performance of the highly permeable grouting material. Its beneficial effects are mainly reflected in the following aspects and are analyzed in combination with the reaction mechanism occurring inside the nano modifier itself.

[0039] The nano modifier is composed of the following components and is prepared by a specific process: Polyurethane emulsion: As the matrix material, it provides good dispersibility and bonding properties.

[0040] Polyvinyl alcohol: Enhances dispersion stability and improves the fluidity of the slurry.

[0041] Ammonium dihydrogen citrate nanoparticles: Provide a filling effect and reduce porosity.

[0042] Sodium carboxyethyl silicate triol particles: Enhance the interfacial bonding force and improve the impermeability performance.

[0043] During the preparation process, the nanoparticles are dispersed in the polyurethane emulsion and undergo chemical reactions with other components at high temperature to form a stable functionalized nanocomposite. Specifically, through the synergistic effect of the polyurethane emulsion and polyvinyl alcohol, the nanoparticles are uniformly dispersed in the liquid phase, avoiding agglomeration, forming a stable slurry system, and improving the fluidity and penetration ability of the slurry.

[0044] The active groups (such as -NH4 + ) on the surface of the ammonium dihydrogen citrate nanoparticles undergo physical adsorption or chemical bonding with the components in the slurry (such as cement hydration products). The carboxyl groups (-COOH) and silanol groups (Si-OH) in the sodium carboxyethyl silicate triol particles can form chemical bonds with the cement matrix, enhancing the interfacial bonding force between the slurry and the substrate and improving the mechanical properties and durability of the solidified body. At high temperature, the functional groups (such as -NCO) in the polyurethane emulsion undergo cross-linking reactions with polyvinyl alcohol or other components to form a three-dimensional network structure, increasing the density of the solidified body, reducing porosity, and improving the impermeability performance and compressive strength.

[0045] The nano modifier significantly improves the comprehensive performance of the grouting material through internal reactions: It improves the fluidity and penetration ability of the slurry, enabling it to effectively fill small cracks and pores.

[0046] Enhances the density and interfacial bonding force of the solidified body, thereby significantly reducing the permeability coefficient and improving the impermeability performance.

[0047] Optimizes the microstructure of the solidified body, making it have higher compressive strength, toughness and durability.

[0048] These beneficial effects make the grouting material of the present invention have a wider applicability and better construction performance in the treatment of seepage and leakage in underground engineering. Description of the Drawings

[0049] Figure 1 It is a scanning electron micrograph of the slurry prepared in Example 5 of the present invention. Detailed Description of the Invention

[0050] The present invention will be further described below in conjunction with specific embodiments.

[0051] Unless otherwise defined, the technical and scientific terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. The following parts by weight can be replaced with the weight unit kilogram when specifically implemented.

[0052] Example 1

[0053] The highly permeable grouting material for the treatment of seepage and leakage diseases, in parts by weight, comprises the following raw materials: 525-type sulfoaluminate cement: 64 parts, fly ash: 30 parts, isophorone diisocyanate: 4 parts, polyvinyl acetate: 20 parts, nano modifier: 8 parts.

[0054] Among them, the parameters of the fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide.

[0055] Among them, the cas number of isophorone diisocyanate is 4098-71-9, and the relative density is 1.049; among them, the cas number of polyvinyl acetate is 9003-20-7, and the relative density is 1.18.

[0056] The preparation method of the nano modifier is as follows: heat the polyurethane emulsion to 40 °C and keep stirring to make it stably dispersed; under the stirring state, slowly drop 0.1 times the weight of the polyurethane emulsion of polyvinyl alcohol, and after the dropping is completed, add 0.1 times the weight of the polyurethane emulsion of diammonium hydrogen citrate nanoparticles and 0.2 times the weight of carboxyethyl silane triol sodium salt particles, and continue to stir for 300 min to make the particles fully dispersed in the polyurethane emulsion; react at 80 °C for 60 min, slowly cool down to room temperature, and stand still, and finally air-dry and dry naturally.

[0057] The preparation method of the highly permeable grouting material for the treatment of seepage and leakage diseases comprises the following steps: raw material weighing and pretreatment: accurately weigh the raw materials according to parts by weight to ensure that all powder raw materials are dry and free of lumps; if there is agglomeration or the particle size does not meet the requirements, perform sieving or grinding treatment.

[0058] Mixing reaction: Weigh the 525-type sulfoaluminate cement, fly ash and nano modifier and place them in a blender. Then add water which is 20 times the weight of the 525-type sulfoaluminate cement. Next, slowly add polyvinyl acetate under stirring conditions to initially form a dispersion. Keep stirring for another 3 minutes, controlling the temperature not to exceed 40°C. Then slowly drop isophorone diisocyanate into the above dispersion according to the formula dosage, and continue stirring for 5 minutes, controlling the temperature at 35°C to obtain a slurry. Then filter the slurry with a filter screen or filter bag for later use.

[0059] Example 2

[0060] The high-permeability grouting material for treating seepage water diseases, by weight, comprises the following raw materials: 90 parts of 525-type sulfoaluminate cement, 15 parts of fly ash, 8 parts of isophorone diisocyanate, 10 parts of polyvinyl acetate, and 20 parts of nano modifier.

[0061] The parameters of the fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide.

[0062] The cas number of the isophorone diisocyanate is 4098-71-9, and the relative density is 1.049.

[0063] The cas number of the polyvinyl acetate is 9003-20-7, and the relative density is 1.18.

[0064] Preferably, the preparation method of the nano modifier is as follows: Heat the polyurethane emulsion to 50°C and keep stirring to make it stably dispersed; under stirring, slowly drop 0.3 times the weight of polyvinyl alcohol into the polyurethane emulsion. After dropping, add 0.1 times the weight of the polyurethane emulsion of ammonium hydrogen citrate nanoparticles and 0.2 times the weight of carboxyethyl silane triol sodium salt particles, and continue stirring for 60 minutes to fully disperse the particles into the polyurethane emulsion; react at 90°C for 30 minutes, slowly cool down to room temperature, and let it stand, and finally air-dry it naturally.

[0065] The preparation method of the high-permeability grouting material for treating seepage water diseases comprises the following steps: Raw material weighing and pretreatment: Accurately weigh the raw materials according to the weight parts to ensure that all powder raw materials are dry and free of lumps; if there is agglomeration or the particle size does not meet the requirements, perform sieving or grinding treatment.

[0066] Mixing reaction: Weigh the Type 525 sulfoaluminate cement, fly ash, and nano modifier and place them in a blender. Then add water that is 20 times the weight of the Type 525 sulfoaluminate cement. Next, slowly add polyvinyl acetate under stirring conditions to initially form a dispersion. Continue stirring for 5 minutes while controlling the temperature not to exceed 40°C. Then slowly drop isophorone diisocyanate into the above dispersion according to the formula dosage and continue stirring for 10 minutes while controlling the temperature at 25°C to obtain a slurry. Then filter the slurry with a filter screen or filter bag for later use.

[0067] Example 3

[0068] A highly permeable grouting material for treating seepage water diseases, in parts by weight, includes the following raw materials: 70 parts of Type 525 sulfoaluminate cement, 25 parts of fly ash, 4 parts of isophorone diisocyanate, 20 parts of polyvinyl acetate, and 14 parts of nano modifier.

[0069] Among them, the parameters of fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide.

[0070] Among them, the cas number of isophorone diisocyanate is 4098 - 71 - 9, and the relative density is 1.049.

[0071] Among them, the cas number of polyvinyl acetate is 9003 - 20 - 7, and the relative density is 1.18.

[0072] Among them, the preparation method of the nano modifier is as follows: Heat the polyurethane emulsion to 40°C and continuously stir to make it stably dispersed; under stirring, slowly drop 0.1 times the weight of polyvinyl alcohol into the polyurethane emulsion. After dropping, add 0.1 times the weight of diammonium hydrogen citrate nanoparticles and 0.2 times the weight of sodium carboxyethyl silicate triol particles of the polyurethane emulsion, and continue stirring for 30 minutes to fully disperse the particles into the polyurethane emulsion; react at 80°C for 30 minutes, slowly cool down to room temperature, and let it stand, and finally air-dry and dry naturally.

[0073] The preparation method of the above-mentioned highly permeable grouting material for treating seepage water diseases includes the following steps: Raw material weighing and pretreatment: Accurately weigh the raw materials according to parts by weight to ensure that all powder raw materials are dry and free of lumps; if there is agglomeration or the particle size does not meet the requirements, perform sieving or grinding treatment.

[0074] Mixing reaction: Weigh the Type 525 sulfoaluminate cement, fly ash, and nano modifier and place them in a mixer. Then add water that is 20 times the weight of the Type 525 sulfoaluminate cement. Next, slowly add polyvinyl acetate under stirring conditions to initially form a dispersion. Continue stirring for 3 minutes, controlling the temperature not to exceed 40°C. Then slowly drop isophorone diisocyanate into the above dispersion according to the formulated dosage, and continue stirring for 5 minutes, controlling the temperature at 25°C to obtain a slurry. Then filter the slurry with a filter screen or filter bag for later use.

[0075] Example 4

[0076] A highly permeable grouting material for treating seepage water diseases, in parts by weight, includes the following raw materials: 80 parts of Type 525 sulfoaluminate cement, 18 parts of fly ash, 8 parts of isophorone diisocyanate, 15 parts of polyvinyl acetate, and 18 parts of nano modifier.

[0077] The parameters of the fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum trioxide is 35%, the mass percentage content of iron trioxide is 15%, and the balance is calcium oxide.

[0078] The cas number of the isophorone diisocyanate is 4098 - 71 - 9, and the relative density is 1.049.

[0079] The cas number of the polyvinyl acetate is 9003 - 20 - 7, and the relative density is 1.18.

[0080] The preparation method of the nano modifier is as follows: Heat the polyurethane emulsion to 50°C and continuously stir to make it stably dispersed; under stirring, slowly drop 0.3 times the weight of the polyurethane emulsion of polyvinyl alcohol. After the dropping is completed, add 0.1 times the weight of the polyurethane emulsion of diammonium hydrogen citrate nanoparticles and 0.2 times the weight of the carboxyethyl silane triol sodium salt particles, and continue stirring for 60 minutes to fully disperse the particles into the polyurethane emulsion; react at 90°C for 60 minutes, slowly cool to room temperature, and let it stand, and finally air-dry and dry naturally.

[0081] The preparation method of the highly permeable grouting material for treating seepage water diseases includes the following steps: Raw material weighing and pretreatment: Accurately weigh the raw materials according to parts by weight to ensure that all powder raw materials are dry and free of lumps; if there is agglomeration or non-compliance with particle size requirements, perform sieving or grinding treatment.

[0082] Mixing reaction: Weigh the Type 525 sulfoaluminate cement, fly ash, and nano-modifier and place them in a blender. Then add water that is 20 times the weight of the Type 525 sulfoaluminate cement. Next, slowly add polyvinyl acetate under stirring conditions to initially form a dispersion. Continue stirring for 5 minutes while controlling the temperature not to exceed 40°C. Then slowly drop isophorone diisocyanate into the above dispersion according to the formula dosage and continue stirring for 10 minutes while controlling the temperature at 35°C to obtain a slurry. Then filter the slurry with a filter screen or filter bag for later use.

[0083] Example 5

[0084] A highly permeable grouting material for treating seepage water diseases, by weight, includes the following raw materials: 75 parts of Type 525 sulfoaluminate cement, 22 parts of fly ash, 6 parts of isophorone diisocyanate, 18 parts of polyvinyl acetate, and 16 parts of nano-modifier.

[0085] The parameters of the fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide.

[0086] The cas number of isophorone diisocyanate is 4098-71-9, and the relative density is 1.049.

[0087] The cas number of polyvinyl acetate is 9003-20-7, and the relative density is 1.18.

[0088] The preparation method of the nano-modifier is as follows: Heat the polyurethane emulsion to 45°C and continuously stir to make it stably dispersed; under stirring, slowly drop 0.2 times the weight of polyvinyl alcohol into the polyurethane emulsion. After the dropping is completed, add 0.1 times the weight of the polyurethane emulsion of ammonium hydrogen citrate nanoparticles and 0.2 times the weight of carboxyethyl silane triol sodium salt particles, and continue stirring for 50 minutes to fully disperse the particles into the polyurethane emulsion; react at 85°C for 50 minutes, slowly cool down to room temperature, and let it stand, and finally air-dry and dry naturally.

[0089] The preparation method of the highly permeable grouting material for treating seepage water diseases includes the following steps: Raw material weighing and pretreatment: Accurately weigh the raw materials according to the weight parts to ensure that all powder raw materials are dry and free of lumps; if there is agglomeration or non-compliance with the particle size requirements, perform sieving or grinding treatment.

[0090] Mixing reaction: Weigh the Type 525 sulfoaluminate cement, fly ash and nano-modifier and place them in a blender. Then add water that is 20 times the weight of the Type 525 sulfoaluminate cement. Next, slowly add polyvinyl acetate under stirring conditions to initially form a dispersion. Keep stirring for another 4 minutes, controlling the temperature not to exceed 40°C. Then slowly drop isophorone diisocyanate into the above dispersion according to the formulated dosage and continue stirring for 8 minutes, controlling the temperature at 30°C to obtain a slurry. Then filter the slurry with a filter screen or filter bag for later use.

[0091] Comparative Example 1

[0092] The high-permeability grouting material for treating seepage water diseases, in parts by weight, comprises the following raw materials: 75 parts of Type 525 sulfoaluminate cement, 22 parts of fly ash, 18 parts of polyvinyl acetate, and 16 parts of nano-modifier.

[0093] Among them, the parameters of the fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide.

[0094] Among them, the cas number of polyvinyl acetate is 9003-20-7 and the relative density is 1.18.

[0095] The preparation method of the nano-modifier is as follows: Heat the polyurethane emulsion to 45°C and keep stirring to make it stably dispersed. Under stirring, slowly drop 0.2 times the weight of the polyurethane emulsion of polyvinyl alcohol into it. After the dropping is completed, add 0.1 times the weight of the polyurethane emulsion of diammonium hydrogen citrate nanoparticles and 0.2 times the weight of the sodium carboxyethyl silicate triol particles, and continue stirring for 50 minutes to fully disperse the particles into the polyurethane emulsion. React at 85°C for 50 minutes, slowly cool down to room temperature, and let it stand, and finally air-dry it naturally.

[0096] The preparation method of the high-permeability grouting material for treating seepage water diseases comprises the following steps: Raw material weighing and pretreatment: Accurately weigh the raw materials according to parts by weight to ensure that all powder raw materials are dry and free of lumps. If there is agglomeration or the particle size does not meet the requirements, perform sieving or grinding treatment.

[0097] Mixing reaction: Weigh the Type 525 sulfoaluminate cement, fly ash and nano-modifier and place them in a blender. Then add water that is 20 times the weight of the Type 525 sulfoaluminate cement. Next, slowly add polyvinyl acetate under stirring conditions to initially form a dispersion. Keep stirring for another 4 minutes, controlling the temperature not to exceed 40°C. Then filter the slurry with a filter screen or filter bag for later use.

[0098] Comparative Example 2

[0099] A highly permeable grouting material for treating seepage water diseases, by weight, includes the following raw materials: 525-type sulfoaluminate cement: 75 parts, fly ash: 22 parts, isophorone diisocyanate: 6 parts, nano modifier: 16 parts.

[0100] Among them, the parameters of the fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide.

[0101] Among them, the cas number of isophorone diisocyanate is 4098-71-9, and the relative density is 1.049.

[0102] The preparation method of the nano modifier is as follows: heat the polyurethane emulsion to 45°C and continuously stir to make it stably dispersed; under stirring, slowly add 0.2 times the weight of the polyurethane emulsion of polyvinyl alcohol, and after the addition is completed, add 0.1 times the weight of the polyurethane emulsion of diammonium hydrogen citrate nanoparticles and 0.2 times the weight of carboxyethyl silane triol sodium salt particles, and continue to stir for 50 min to fully disperse the particles into the polyurethane emulsion; react at 85°C for 50 min, slowly cool down to room temperature, and let it stand, and finally air-dry and dry.

[0103] The preparation method of the highly permeable grouting material for treating seepage water diseases includes the following steps: raw material weighing and pretreatment: accurately weigh the raw materials according to the weight parts to ensure that all powder raw materials are dry and free of lumps; if there is agglomeration or non-compliance with the particle size requirements, perform sieving or grinding treatment.

[0104] Mixing and reaction: Place the weighed 525-type sulfoaluminate cement, fly ash and nano modifier in a mixer, then add 20 times the weight of the 525-type sulfoaluminate cement of water, continue to stir for 4 min, control the temperature not to exceed 40°C, and then slowly add the isophorone diisocyanate according to the formula dosage to the above dispersion liquid, continue to stir for 8 min, control the temperature to 30°C, obtain a slurry, and then filter the slurry with a filter screen or filter bag for later use.

[0105] Comparative Example 3

[0106] A highly permeable grouting material for treating seepage water diseases, by weight, includes the following raw materials: 525-type sulfoaluminate cement: 75 parts, fly ash: 22 parts, isophorone diisocyanate: 6 parts, polyvinyl acetate: 18 parts.

[0107] Among them, the parameters of the fly ash are as follows: the mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide.

[0108] Among them, the CAS number of isophorone diisocyanate is 4098-71-9, and the relative density is 1.049.

[0109] Among them, the CAS number of polyvinyl acetate is 9003-20-7, and the relative density is 1.18.

[0110] The preparation method of the high-permeability grouting material for treating seepage water diseases includes the following steps: Raw material weighing and pretreatment: Accurately weigh the raw materials according to weight parts to ensure that all powder raw materials are dry and free of lumps; if there is agglomeration or the particle size does not meet the requirements, perform sieving or grinding treatment.

[0111] Mixing reaction: Place the weighed 525-type sulfoaluminate cement and fly ash in a mixer, then add water 20 times the weight of the 525-type sulfoaluminate cement, and then slowly add polyvinyl acetate under stirring conditions to form a dispersion liquid initially. Continue to stir for 4 minutes, control the temperature not to exceed 40 °C, and then slowly drop the isophorone diisocyanate according to the formula dosage into the above dispersion liquid, continue to stir for 8 minutes, control the temperature at 30 °C to obtain a slurry, and then filter the slurry with a filter screen or filter bag for later use.

[0112] Performance testing of the product: (1) Fluidity testing

[0113] Fluidity testing is used to evaluate the flow and filling ability of the grouting slurry, and is a key index for whether the grouting material can smoothly penetrate into cracks and pores. The specific testing methods and standards are as follows: Fluidity determination: Use a standard fluidity cone to measure the spread diameter of the freshly mixed slurry on a vibrating table. Place the fluidity cone on a horizontal glass plate with the cone opening facing down, and add the slurry into the cone; slowly lift the cone cylinder to allow the slurry to flow and spread naturally on the glass plate; start the vibrating table, stop after vibrating 15 times, and measure the maximum diameter and vertical diameter of the slurry spread. The fluidity is the average of the two diameters and is expressed in millimeters (mm).

[0114] Marsh cone outflow time determination: The Marsh cone outflow time is another index to characterize the fluidity of the grouting slurry. During the test, pour the slurry into the Marsh cone, wait for it to flow out naturally, and record the time required for 1500 mL of the slurry to flow out.

[0115] Table 1 Fluidity test results

[0116]

[0117] Flowability (mm): In the example group, the flowability was between 172.3 - 179.6 mm, indicating that the slurry had good fluidity and was suitable for penetrating into fine cracks. In the comparative example group, the flowability decreased significantly. Especially for Comparative Example 3, it was only 153.1 mm, indicating that after removing key components (such as nano-modifiers), the fluidity of the slurry decreased significantly, which was not conducive to construction.

[0118] Marsh cone outflow time (s): In the example group, the outflow time was between 26.4 - 27.3 seconds, showing low viscosity characteristics, which helped the slurry to be quickly injected into the cracks. In the comparative example group, the outflow time increased significantly. Especially for Comparative Example 3, it reached 35.9 s, indicating that the viscosity of the slurry was too high, which was not conducive to penetration construction.

[0119] Comprehensive evaluation: Example 5 performed the best. It had the highest flowability (179.6 mm) and the shortest Marsh cone outflow time (26.4 s), indicating that its formula had excellent fluidity after optimization.

[0120] The performance deterioration of the comparative example group indicated that key components (isophorone diisocyanate, polyvinyl acetate, nano-modifiers) were crucial for maintaining the low viscosity and high fluidity of the slurry.

[0121] (2) Permeability test

[0122] Permeability reflects the diffusion and filling ability of grouting materials in different media. By conducting grouting experiments in standard sand columns or clay media, the permeability of the materials can be comprehensively evaluated.

[0123] Standard sand column permeability experiment: Standard sand with a particle size distribution and compaction density meeting the requirements was selected to prepare a cylindrical sand column with a diameter of 10 cm and a height of 50 cm. A grouting experiment was carried out under unconfined conditions: a grouting pipe was arranged at the bottom of the sand column, and the slurry was slowly injected until the slurry overflowed from the top of the sand column. After the slurry solidified, the sand column was taken out and cut to observe the diffusion range of the slurry. Permeability coefficient determination: The permeability of the sand column was tested before and after grouting, and the Darcy's law formula was used to calculate the change in the permeability coefficient.

[0124] The parameter conditions of the standard sand are as follows: d10 (effective particle size): 0.15 - 0.30 mm, that is, on the particle size distribution curve, the particle content less than this particle size accounts for 10% of the total mass; d30: 0.35 - 0.55 mm, that is, on the particle size distribution curve, the particle content less than this particle size accounts for 30% of the total mass; d60 (limiting particle size): 0.6 - 0.9 mm, that is, on the particle size distribution curve, the particle content less than this particle size accounts for 60% of the total mass. As can be seen from the above, the effective particle size d10 of the standard sand is in the range of 0.15 - 0.30 mm, and d60 is in the range of 0.6 - 0.9 mm. The overall particle size range is relatively narrow, belonging to medium sand.

[0125] Table 2 Permeability Test Results

[0126]

[0127] Analysis and Evaluation

[0128] Diffusion radius (cm): In the example group, the diffusion radius is between 25 - 29 cm, all showing good penetration and diffusion ability. Especially for Example 5, it reaches 29 cm, indicating that its material can effectively fill cracks and pores. In the comparative example group, the diffusion radius is significantly reduced. For Comparative Example 3, it is only 15 cm, indicating that the material loses its good penetration and diffusion ability after removing the nano - modifier.

[0129] Permeability coefficient: In the example group, the permeability coefficient is significantly reduced to 3 - 5×10 -7 cm / s, indicating that the anti - permeability performance of the medium after grouting has been greatly improved. In the comparative example group, the permeability coefficient increases significantly, indicating that the material cannot effectively reduce the permeability of the medium after removing the key components.

[0130] Comprehensive evaluation: Example 5 performs the best. It has the largest diffusion radius (29 cm) and the lowest permeability coefficient, indicating its excellent penetration performance and anti - permeability effect. The performance deterioration of the comparative example group verifies the importance of the key components again. Especially after removing the nano - modifier, both the diffusion radius and the anti - permeability performance of Comparative Example 3 decrease significantly.

[0131] According to the experimental results, it is recommended to adopt the formula of Example 5 in actual engineering, and at the same time, strictly control the addition amount of key components to ensure that the grouting material has good construction adaptability and long - term anti - permeability effect. As Figure 1 shown, it shows the condition diagram of the slurry prepared in Example 5 after 28 - day curing (curing temperature: 25℃, curing humidity: 95%), and a dense microstructure can be seen.

[0132] In Comparative Example 1, the removal of isophorone diisocyanate (IPDI) led to a significant decline in material properties, and the mechanism can be attributed to the following points: Reduction in the strength of the cured body: After the absence of IPDI, the slurry could not form an efficient cross-linked network, and the mechanical properties of the cured body decreased significantly. The internal structure of the cured body became loose, resulting in a weakened load-bearing capacity. Decline in impermeability: The cross-linking effect of IPDI could significantly reduce the porosity inside the material. After removal, a dense structure could not be formed in the cured body, the porosity increased, and the permeability coefficient increased. As shown in the permeability test, the permeability coefficient of Comparative Example 1 was much higher than that of Example 5. Weakening of material durability: IPDI has excellent ultraviolet and chemical corrosion resistance. After removal, the material was more vulnerable to environmental factors (such as water, acids and alkalis, ultraviolet rays) during long-term use and deteriorated. After the removal of IPDI, significant changes occurred in the microstructure of the slurry cured body: Increase in pores: After the lack of cross-linking reaction, microcracks and pores were easily generated during the curing process of the slurry. Weakening of interfacial bonding force: The synergistic effect of IPDI and polyvinyl acetate could enhance the bonding force between particles. After removal, the bonding force in the interfacial transition zone was insufficient, resulting in an uneven overall structure.

[0133] In Comparative Example 2, the removal of polyvinyl acetate led to a significant decline in material properties, and the mechanism can be attributed to the following points: Reduction in slurry fluidity: After the absence of polyvinyl acetate, the slurry lost the lubrication effect of molecular chains, the internal friction increased, and the fluidity decreased significantly. As shown in the fluidity test, the fluidity of Comparative Example 2 was 165 mm, much lower than that of Example 5 (179.6 mm), and the Marsh cone outflow time increased to 31.7 s, indicating an increase in the slurry viscosity, which was not conducive to construction. Weakening of the interfacial bonding force of the cured body: After the removal of polyvinyl acetate, the interfacial bonding force between the slurry and the substrate decreased significantly, resulting in weak bonding between the particles inside the cured body. This directly affected the compressive strength and durability of the cured body. Increase in porosity: The absence of the polyvinyl acetate network structure resulted in more micropores generated during the curing process, leading to a decrease in density. In the permeability test, the permeability coefficient of Comparative Example 2 was significantly higher than that of Example 5, indicating a serious decline in impermeability. Decline in toughness and crack resistance: After the absence of the flexible polyvinyl acetate molecular chain, the cured body was prone to cracks due to dry shrinkage or external loads, thereby reducing the stability during long-term use. After the removal of polyvinyl acetate, significant changes occurred in the microstructure of the slurry cured body: Uneven particle distribution: After the absence of the auxiliary dispersion function of polyvinyl acetate, cement particles and fly ash were prone to agglomeration in the slurry. Increase in pores: Due to the lack of a uniformly distributed network structure, the porosity inside the cured body increased. Deterioration of the interfacial transition zone: The interfacial bonding force between the slurry and the substrate weakened, making the transition zone a weak link.

[0134] Comparative Example 3 removed the nano-modifier, resulting in a significant decline in the performance of the grouting material. The mechanism can be attributed to the following points: - Decrease in slurry fluidity: - Mechanism: The functional polyurethane emulsion and polyvinyl alcohol in the nano-modifier can improve the lubrication performance of the slurry. After removal, the internal friction of the slurry increases and the fluidity decreases. - Performance: In the fluidity test, the fluidity of Comparative Example 3 was 153.1 mm, much lower than that of Example 5 (179.6 mm), and the Marsh cone outflow time increased significantly to 35.9 s (26.4 s for Example 5). - Decrease in the density of the solidified body: - Mechanism: Nano-particles have a filling effect and can reduce the micro-pores inside the material. After removal, the porosity in the solidified body increases, resulting in a decrease in density. - Performance: In the permeability test, the permeability coefficient of Comparative Example 3 was too high, leading to a significant decline in its impermeability performance. - Weakening of the interfacial bonding force: - Mechanism: The nano-modifier enhances the interfacial bonding force between the slurry and the substrate through chemical reactions or physical adsorption. After removal, the interfacial bonding force is insufficient, resulting in a decrease in the strength of the solidified body. - Performance: The diffusion radius was only 15 cm (29 cm for Example 5), indicating a significant decline in the slurry penetration ability and filling effect. - Deterioration of mechanical properties: - Mechanism: Nano-particles form a network structure during the curing process, which helps to improve the compressive strength and toughness. After removal, the internal structure of the solidified body is loose and the compressive strength is significantly reduced. - Performance: The solidified body is prone to cracking or damage and is not suitable for complex engineering environments. After removing the nano-modifier, the microstructure of the slurry solidified body changes significantly: - Increase in porosity: More micro-pores appear inside the solidified body due to the lack of the filling effect of nano-particles. - Uneven particle distribution: In the absence of the functional polyurethane emulsion and polyvinyl alcohol, cement particles and fly ash are prone to agglomeration, resulting in uneven material distribution. - Deterioration of the interfacial transition zone: The weakening of the interfacial bonding force makes the transition zone a weak link.

[0135] The above content further elaborates on the present invention in combination with specific embodiments. It cannot be determined that the specific implementation of the present invention is only limited to these descriptions. For those of ordinary skill in the technical field of energy-saving and environmental protection building materials to which the present invention pertains, without departing from the concept of the present invention, several simple deductions or substitutions can still be made, which should all be regarded as falling within the protection scope determined by the claims submitted for the present invention.

Claims

1. A highly permeable grouting material for treating seepage water diseases, characterized in that: By weight, it includes the following raw materials: 525-type sulfoaluminate cement: 64 parts - 90 parts, fly ash: 15 parts - 30 parts, isophorone diisocyanate: 4 parts - 8 parts, polyvinyl acetate: 10 parts - 20 parts, nano modifier: 8 parts - 20 parts; The preparation method of the nano modifier is as follows: Heat the polyurethane emulsion to 40 - 50 °C and continuously stir to make it stably dispersed; Under stirring, slowly add 0.1 times - 0.3 times its weight of polyvinyl alcohol to the polyurethane emulsion. After the addition is completed, add 0.1 times the weight of the polyurethane emulsion of diammonium hydrogen citrate nanoparticles and 0.2 times the weight of sodium carboxyethyl silane triol salt particles, and continue to stir for 30 - 60 min to fully disperse the particles into the polyurethane emulsion; React at 80 - 90 °C for 30 - 60 min, slowly cool down to room temperature, and let it stand, and finally perform natural air drying.

2. The highly permeable grouting material for treating seepage and leakage diseases according to claim 1, wherein: By weight, it includes the following raw materials: 525-type sulfoaluminate cement: 70 parts - 80 parts, fly ash: 18 parts - 25 parts, isophorone diisocyanate: 4 parts - 8 parts, polyvinyl acetate: 15 parts - 20 parts, nano modifier: 14 parts - 18 parts.

3. The highly permeable grouting material for treating seepage water damage according to claim 2, characterized in that: By weight, it includes the following raw materials: 525-type sulfoaluminate cement: 75 parts, fly ash: 22 parts, isophorone diisocyanate: 6 parts, polyvinyl acetate: 18 parts, nano modifier: 16 parts.

4. The highly permeable grouting material for treating seepage water diseases according to claim 1, characterized in that: The parameters of the fly ash are as follows: The mass percentage content of silicon dioxide is 45%, the mass percentage content of aluminum oxide is 35%, the mass percentage content of iron oxide is 15%, and the balance is calcium oxide.

5. The highly permeable grouting material for treating seepage water diseases according to claim 1, characterized in that: The cas number of isophorone diisocyanate is 4098-71-9, and the relative density is 1.049; The cas number of polyvinyl acetate is 9003-20-7, and the relative density is 1.

18.

6. The preparation method of the highly permeable grouting material for treating seepage water diseases as described in claim 1 includes the following steps: Weighing and pretreatment of raw materials: Weigh the raw materials accurately according to weight to ensure that all powder raw materials are dry and free of lumps; If there is agglomeration or the particle size does not meet the requirements, perform sieving or grinding treatment; Mixing reaction: Place the weighed 525-type sulfoaluminate cement, fly ash and nano modifier in a mixer, then add 20 times the weight of water of the 525-type sulfoaluminate cement, and then slowly add polyvinyl acetate under stirring to initially form a dispersion liquid. Continue to stir for 3 - 5 min, control the temperature not to exceed 40 °C, and then slowly add isophorone diisocyanate dropwise to the above dispersion liquid according to the formula dosage, and continue to stir for 5 - 10 min, control the temperature at 25 - 35 °C to obtain a slurry, and then filter the slurry with a filter screen or filter bag for use.

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