High-strength and durable grouting material, preparation method and application thereof

Abstract

The application relates to the technical field of building materials, and particularly discloses a high-strength and durable grouting material as well as a preparation method and application thereof. The high-strength and durable grouting material provided by the application introduces hydroxyl fatty acid-nano oxide, the existence of the hydroxyl fatty acid can effectively improve the dispersion stability of the nano oxide in a cement matrix, microdefects are avoided, and the hydroxyl fatty acid can be directionally migrated to pore inner walls and an aggregate / steel interface in a hydration process, a dense and hydrophobic molecular film layer is constructed in situ, and multiple performance synergistic improvements are simultaneously realized; the hydroxyl fatty acid-nano oxide and amorphous aluminosilicate microspheres are simultaneously introduced, the pore structure can be effectively refined, the connected capillary pores can be blocked, the chloride ion diffusion and early self-shrinkage can be significantly reduced, and the synergistic improvements of high strength, frost resistance, impermeability, low-temperature resistance, micro-expansion and excellent fluidity are realized.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, and in particular to a high-strength and durable grouting material, its preparation method, and its application. Background Technology

[0002] Grouting materials, used for filling voids and transferring loads in equipment foundations, prestressed ducts, and steel column bases, are widely applied in critical areas such as prestressed duct filling, secondary grouting of equipment foundations, bridge bearing installation, prefabricated building joint connections, and concrete structure reinforcement and repair. Their mechanical properties, volumetric stability, durability, and workability directly affect the safety and service life of the structure. Traditional cement-based grouting materials typically use silicate cement as the main binder, supplemented with fine aggregates, expanding agents, and water-reducing agents. However, these materials generally suffer from slow early strength development, low later strength, significant drying shrinkage or autogenous shrinkage, poor impermeability, and insufficient durability under corrosive environments such as chloride ions and sulfates. Especially in marine engineering, chemical plants, freeze-thaw cycles, or high-humidity salt spray environments, ordinary grouting materials are prone to cracking, spalling, and steel corrosion, failing to meet the long-term reliability requirements of modern high-performance engineering structures.

[0003] In recent years, to improve the overall performance of grouting materials, researchers have attempted to introduce mineral admixtures (such as silica fume, fly ash, and slag powder), polymer emulsions, nanomaterials (such as nano-silica and carbon nanotubes), as well as high-efficiency water-reducing agents and expansion-regulating components. While these modification methods have improved the fluidity and strength of grouting materials to some extent, technical bottlenecks remain in achieving a synergistic effect of multiple objectives, including ultra-high strength, low shrinkage, excellent resistance to chloride ion penetration, freeze-thaw cycle resistance, and long-term volume stability. Furthermore, some high-performance grouting materials suffer from high cost, complex processes, short working time, or insufficient bonding performance with reinforcing steel, limiting their widespread application in practical engineering projects.

[0004] Therefore, there is an urgent need to develop a new type of grouting material that combines high strength, high durability, micro-expansion, good fluidity, and construction adaptability. It can not only quickly obtain high strength in normal or low temperature environments, but also maintain structural integrity and functionality for a long time in harsh service environments. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a high-strength and durable grouting material, its preparation method, and its application. By introducing hydroxy fatty acid nano-oxides and amorphous aluminosilicate microspheres, the pore structure is effectively refined and the interconnected capillaries are blocked, significantly reducing chloride ion diffusion and early self-shrinkage. This achieves a synergistic improvement in high strength (≥100 MPa), high durability (freezing resistance, impermeability, and low-temperature resistance), micro-expansion, and excellent flowability.

[0006] To achieve the above-mentioned objectives, the embodiments of the present invention employ the following technical solutions: In a first aspect, the present invention provides a high-strength and durable grouting material, comprising hydroxy fatty acid nano-oxides and amorphous aluminosilicate microspheres; The hydroxy fatty acids in the hydroxy fatty acid nano-oxide include one or more of ricinoleic acid, thiolactic acid, or 12-hydroxystearic acid. The hydroxy fatty acid nano-oxides include one or more of nano-ZnO, nano-MgO, nano-CaO, nano-Al2O3, nano-TiO2, or nano-ZrO2.

[0007] Preferably, the mass ratio of nano-oxide to hydroxy fatty acid in the hydroxy fatty acid-nano-oxide is 1:1.2~2.0.

[0008] Compared to existing technologies, the high-strength and durable grouting material provided by this invention introduces hydroxy fatty acid nano-oxides. The hydroxy fatty acids are anchored to the surface of the nano-oxides via carboxyl groups, with long-chain alkyl groups extending outwards, forming a dual barrier of steric hindrance and electrostatic repulsion. This prevents nanoparticles from agglomerating in the high-ionic-strength cement pore liquid, effectively solving the problem of nanoparticle agglomeration and thus reducing strength loss. During cement hydration, the hydroxy fatty acids self-assemble on the inner wall of the pores, forming a monomolecular hydrophobic film, transforming the pore wall from hydrophilic to hydrophobic, significantly reducing capillary water absorption and Cl-. - It can penetrate and reduce frost heave pressure; in addition, hydroxy fatty acids can work synergistically with polycarboxylate superplasticizers to reduce the adsorption loss of polycarboxylate by nanoparticles, reduce the yield stress of slurry, improve fluidity retention, and meet the needs of pumping and gravity injection.

[0009] Preferably, the preparation method of the hydroxy fatty acid-nano oxide includes the following steps: dissolving hydroxy fatty acid in an organic solvent, adding nano oxide, and shearing to obtain hydroxy fatty acid-nano oxide.

[0010] More preferably, the organic solvent is anhydrous ethanol. The present invention does not have a special limitation on the amount of the organic solvent used, as long as it can completely dissolve the hydroxy fatty acids.

[0011] Preferably, the method for preparing the amorphous aluminosilicate microspheres includes the following steps: The metakaolin suspension was mixed with silica sol and sodium aluminate solution to obtain a homogenate; After homogenization and granulation, amorphous aluminosilicate microspheres were obtained by calcination.

[0012] Preferably, based on the mass of metakaolin, the mass ratio of the metakaolin suspension to the silica sol and sodium aluminate solution is 100:100~200:50~125; and the particle size of the amorphous aluminosilicate microspheres is 5~8μm.

[0013] Preferably, the calcination temperature is 620℃~675℃ and the duration is 1.5~2.5h.

[0014] In this invention, calcination temperatures above 750°C will generate mullite, causing the microspheres to lose their reactivity. The amorphous aluminosilicate microspheres prepared by this invention can be directly used as functional mineral admixtures in high-strength grouting materials.

[0015] Preferably, the mass concentration of the metakaolin suspension is 30% to 50%; and the solid content of the homogenate is 30% to 45%.

[0016] In this invention, if the concentration of the metakaolin suspension and homogenate is too low, the microspheres will have a high hollow rate and low strength; if the concentration is too high, the nozzles will easily become clogged and the green spheres will crack during granulation. This invention adjusts the concentration of the metakaolin suspension and homogenate to ensure stable atomization during the granulation process, ultimately resulting in the formation of dense microspheres through calcination.

[0017] Preferably, by weight, the high-strength durable grout comprises 590-630 parts of sulfoaluminate cement, 70-110 parts of silicate cement, 95-115 parts of silica fume, 45-65 parts of amorphous aluminosilicate microspheres, 2.2-3.8 parts of hydroxy fatty acid nano-oxide, 0.8-1.5 parts of 4,4′-oxobisbenzenesulfonyl hydrazine, 15-25 parts of lightly calcined MgO, 1010-1070 parts of quartz sand, 19-23 parts of polycarboxylate superplasticizer, 0.1-0.25 parts of defoamer, and 152-162 parts of water.

[0018] In this invention, sulfoaluminate cement provides early rapid hardening and micro-expansion characteristics in the grout, while silicate cement enhances later strength stability. The combination of the two forms an early-strength-later-strength bimodal hydration sequence, providing a strength framework for the system. Silica fume fills nanopores, and amorphous aluminosilicate microspheres release moisture through internal curing to inhibit self-shrinkage. Furthermore, their high specific surface area and alumina active sites adsorb Cl... - Simultaneously, the slow-release silica-alumina components participate in the later-stage volcanic ash reaction in an alkaline environment, continuously improving density. Hydroxy fatty acid nano-oxides can immediately saponify in the alkaline porous solution to generate nano-sized calcium / zinc soap crystals, which, together with silica fume, form the first impermeability barrier. 4,4′-oxobisbenzenesulfonyl hydrazine releases uniformly distributed micron-sized closed pores during the plastic stage, providing plastic expansion, preventing settling gaps, and effectively improving resistance to freeze-thaw cycles. Lightly calcined MgO continuously hydrates in the later stages to generate Mg(OH)2, providing long-term expansion, compensating for drying shrinkage, and its weak alkalinity can also buffer chloride ion corrosion.

[0019] By combining polycarboxylate superplasticizer with trace amounts of defoamer, the gas-containing structure can be precisely controlled while ensuring high fluidity.

[0020] The low water-cement ratio, combined with the aforementioned multiple pore-blocking, hydrophobic, and expansion mechanisms, enables the material to be pumped for construction even at -10℃. The chloride ion diffusion coefficient is significantly reduced after 28 days, and the relative dynamic elastic modulus remains ≥90% after freeze-thaw cycles, achieving a combination of high strength, high durability, low temperature resistance, and impermeability.

[0021] Secondly, the present invention provides a method for preparing the high-strength and durable grouting material described in the above technical solution, comprising the following steps: Sulfoaluminate cement, silicate cement, silica fume, amorphous aluminosilicate microspheres, quartz sand and lightly calcined MgO are mixed to obtain the first mixture; The first mixture was stirred evenly with hydroxy fatty acid nano-oxide and 4,4′-oxobisbenzenesulfonylhydrazine to obtain a dry material. Polycarboxylate superplasticizer, defoamer and water are mixed evenly to obtain a liquid phase; High-strength and durable grouting material is obtained by mixing the liquid phase with the dry material.

[0022] Thirdly, the present invention provides the application of the high-strength durable grouting material described in the above-mentioned technical solution or the high-strength durable grouting material prepared by the preparation method of the high-strength durable grouting material described in the above-mentioned technical solution in operations in extremely cold or highly permeable environments.

[0023] The beneficial effects of this invention are: The high-strength and durable grout of this invention introduces hydroxy fatty acid nano-oxides, which effectively improves the dispersion stability of nano-oxides in the cement matrix, avoids the generation of micro-defects, and can also migrate directionally to the inner wall of pores and the aggregate / reinforcing steel interface during hydration, thereby constructing a dense and hydrophobic molecular film layer in situ, thus achieving multiple performance synergistic improvements simultaneously.

[0024] Amorphous aluminosilicate microspheres possess internal curing, ion adsorption, and post-ferroash activity. Their porous amorphous structure effectively stores and slowly releases moisture during the early stages of cement hydration, significantly inhibiting early self-shrinkage caused by self-drying in high-cementing-strength material systems and reducing the risk of microcracks. Simultaneously, the aluminum-oxygen tetrahedra and silanol sites on the microsphere surface exhibit strong chemisorption capacity for chloride ions, actively capturing and immobilizing invading Cl- ions. - It can slow down the corrosion process of steel bars; in an alkaline porous environment, amorphous aluminosilicate microspheres can also dissolve and release active SiO2 and Al2O3, participate in the generation of additional CASH or NASH gels, continuously fill the interfacial micropores, and improve the later strength and matrix density.

[0025] This invention enables grouting materials to possess ultra-high strength, ultra-low permeability, excellent freeze-thaw resistance, and long-term volume stability in extreme environments such as frigid and high-chlorine marine environments through multi-scale synergy of chemical activity, physical filling, interface regulation, and pore structure optimization. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0027] Unless otherwise specified, all materials used in this invention are commercially available products.

[0028] Example 1 This embodiment provides a high-strength and durable grouting material, which, by weight, consists of 610 parts of sulfoaluminate cement, 90 parts of silicate cement, 105 parts of silica fume, 55 parts of amorphous aluminosilicate microspheres, 3.0 parts of hydroxy fatty acid nano-oxide, 1.2 parts of 4,4′-oxobisbenzenesulfonyl hydrazine, 20 parts of lightly calcined MgO, 1040 parts of quartz sand, 21 parts of polycarboxylate superplasticizer, 0.18 parts of defoamer, and 157 parts of water.

[0029] The preparation method of the above-mentioned hydroxy fatty acid nano-oxide includes the following steps: 3g of ricinoleic acid was dissolved in 30g of anhydrous ethanol. 3g of nano-ZnO was added while stirring in a 60℃ water bath at 500rpm. After shearing for 10min, the ethanol was recovered by vacuum rotary evaporation at 70℃ to obtain hydroxy fatty acid nano-oxide.

[0030] The preparation method of the above-mentioned amorphous aluminosilicate microspheres includes the following steps: Take 100g of metakaolin, add 145g of deionized water, and stir at 3000rpm for 10min to form a uniform suspension; slowly add 100g of silica sol and 60.0g of sodium aluminate solution, and continue stirring for 30min to obtain a homogenate; spray granulate the homogenate to obtain microspheres with a diameter of 5~8μm, spread the microspheres evenly on a ceramic crucible, put it in a muffle furnace, heat to 650℃ at a heating rate of 2℃ / min, hold for 2h, turn off the power, cool to below 100℃ and take out to obtain amorphous aluminosilicate microspheres.

[0031] The preparation method of the above-mentioned high-strength and durable grouting material includes the following steps: Sulfoaluminate cement, silicate cement, silica fume, amorphous aluminosilicate microspheres, quartz sand and lightly calcined MgO were mixed and stirred at 60 rpm for 2 min to obtain the first mixture; The first mixture was mixed with hydroxy fatty acid nano-oxide and 4,4′-oxobisbenzenesulfonyl hydrazine and stirred at 120 rpm for 1.5 min to obtain a dry material; Polycarboxylate superplasticizer, defoamer and water are mixed evenly to obtain a liquid phase; The liquid phase and dry material are mixed, stirred at 60 rpm for 30 seconds, and then stirred at 240 rpm for 4 minutes to obtain a high-strength and durable grout.

[0032] Example 2 This embodiment provides a high-strength and durable grouting material, which, by weight, consists of 620 parts of sulfoaluminate cement, 80 parts of silicate cement, 110 parts of silica fume, 50 parts of amorphous aluminosilicate microspheres, 2.5 parts of hydroxy fatty acid nano-oxide, 1.0 part of 4,4′-oxobisbenzenesulfonyl hydrazine, 22 parts of lightly calcined MgO, 1050 parts of quartz sand, 22 parts of polycarboxylate superplasticizer, 0.2 parts of defoamer, and 160 parts of water.

[0033] The preparation method of the above-mentioned hydroxy fatty acid nano-oxide includes the following steps: 3g of thiolactic acid was dissolved in 30g of anhydrous ethanol. 3g of nano-MgO was added while stirring in a 60℃ water bath at 450rpm. After shearing for 8min, the ethanol was recovered by vacuum rotary evaporation at 70℃ to obtain hydroxy fatty acid nano-oxide.

[0034] The preparation method of the above-mentioned amorphous aluminosilicate microspheres includes the following steps: Take 100g of metakaolin, add 155g of deionized water, and stir at 2500rpm for 10min to form a uniform suspension; slowly add 120g of silica sol and 50.0g of sodium aluminate solution, and continue stirring for 30min to obtain a homogenate; spray granulate the homogenate to obtain microspheres with a diameter of 5~8μm, spread the microspheres evenly on a ceramic crucible, place it in a muffle furnace, heat to 650℃ at a heating rate of 2℃ / min, hold for 2h, turn off the power, cool to below 100℃ and take out to obtain amorphous aluminosilicate microspheres.

[0035] The preparation method of the above-mentioned high-strength and durable grouting material includes the following steps: Sulfoaluminate cement, silicate cement, silica fume, amorphous aluminosilicate microspheres, quartz sand and lightly calcined MgO were mixed and stirred at 60 rpm for 2 min to obtain the first mixture; The first mixture was mixed with hydroxy fatty acid nano-oxide and 4,4′-oxobisbenzenesulfonyl hydrazine and stirred at 120 rpm for 1.5 min to obtain a dry material; Polycarboxylate superplasticizer, defoamer and water are mixed evenly to obtain a liquid phase; The liquid phase and dry material are mixed, stirred at 60 rpm for 30 seconds, and then stirred at 240 rpm for 4 minutes to obtain a high-strength and durable grout.

[0036] Example 3 This embodiment provides a high-strength and durable grouting material, which, by weight, consists of 590 parts of sulfoaluminate cement, 110 parts of silicate cement, 95 parts of silica fume, 45 parts of amorphous aluminosilicate microspheres, 2.2 parts of hydroxy fatty acid nano-oxide, 0.8 parts of 4,4′-oxobisbenzenesulfonyl hydrazine, 15 parts of lightly calcined MgO, 1010 parts of quartz sand, 19 parts of polycarboxylate superplasticizer, 0.1 parts of defoamer, and 152 parts of water.

[0037] The preparation method of the above-mentioned hydroxy fatty acid nano-oxide includes the following steps: 3g of ricinoleic acid was dissolved in 30g of anhydrous ethanol. 3g of nano-CaO was added while stirring in a 60℃ water bath at 500rpm. After shearing for 10min, the ethanol was recovered by vacuum rotary evaporation at 70℃ to obtain hydroxy fatty acid nano-oxide.

[0038] The preparation method of the above-mentioned amorphous aluminosilicate microspheres includes the following steps: Take 100g of metakaolin, add 155g of deionized water, and stir at 2500rpm for 10min to form a uniform suspension; slowly add 180g of silica sol and 75.0g of sodium aluminate solution, and continue stirring for 30min to obtain a homogenate; spray granulate the homogenate to obtain microspheres with a diameter of 5~8μm, spread the microspheres evenly on a ceramic crucible, place it in a muffle furnace, heat to 675℃ at a heating rate of 2℃ / min, hold for 1.5h, turn off the power, cool to below 100℃ and take out to obtain amorphous aluminosilicate microspheres.

[0039] The preparation method of the above-mentioned high-strength and durable grouting material includes the following steps: Sulfoaluminate cement, silicate cement, silica fume, amorphous aluminosilicate microspheres, quartz sand and lightly calcined MgO were mixed and stirred at 60 rpm for 2 min to obtain the first mixture; The first mixture was mixed with hydroxy fatty acid nano-oxide and 4,4′-oxobisbenzenesulfonyl hydrazine and stirred at 120 rpm for 1.5 min to obtain a dry material; Polycarboxylate superplasticizer, defoamer and water are mixed evenly to obtain a liquid phase; The liquid phase and dry material are mixed, stirred at 60 rpm for 30 seconds, and then stirred at 240 rpm for 4 minutes to obtain a high-strength and durable grout.

[0040] Example 4 This embodiment provides a high-strength and durable grouting material, which, by weight, consists of 630 parts of sulfoaluminate cement, 70 parts of silicate cement, 115 parts of silica fume, 65 parts of amorphous aluminosilicate microspheres, 3.8 parts of hydroxy fatty acid nano-oxide, 1.5 parts of 4,4′-oxobisbenzenesulfonyl hydrazine, 25 parts of lightly calcined MgO, 1070 parts of quartz sand, 23 parts of polycarboxylate superplasticizer, 0.25 parts of defoamer, and 162 parts of water.

[0041] The preparation method of the above-mentioned hydroxy fatty acid nano-oxide includes the following steps: 3g of 12-hydroxystearic acid was dissolved in 30g of anhydrous ethanol. 3g of nano-Al2O3 was added while stirring in a 60℃ water bath at 480rpm. After shearing for 10min, the ethanol was recovered by vacuum rotary evaporation at 70℃ to obtain hydroxy fatty acid nano-oxide.

[0042] The preparation method of the above-mentioned amorphous aluminosilicate microspheres includes the following steps: Take 100g of metakaolin, add 155g of deionized water, and stir at 2000rpm for 10min to form a uniform suspension; slowly add 120g of silica sol and 120.0g of sodium aluminate solution, and continue stirring for 30min to obtain a homogenate; spray granulate the homogenate to obtain microspheres with a diameter of 5~8μm, spread the microspheres evenly on a ceramic crucible, place it in a muffle furnace, heat to 610℃ at a heating rate of 2℃ / min, hold for 2.5h, turn off the power, cool to below 100℃ and take out to obtain amorphous aluminosilicate microspheres.

[0043] The preparation method of the above-mentioned high-strength and durable grouting material includes the following steps: Sulfoaluminate cement, silicate cement, silica fume, amorphous aluminosilicate microspheres, quartz sand and lightly calcined MgO were mixed and stirred at 60 rpm for 2 min to obtain the first mixture; The first mixture was mixed with hydroxy fatty acid nano-oxide and 4,4′-oxobisbenzenesulfonyl hydrazine and stirred at 120 rpm for 1.5 min to obtain a dry material; Polycarboxylate superplasticizer, defoamer and water are mixed evenly to obtain a liquid phase; The liquid phase and dry material are mixed, stirred at 60 rpm for 30 seconds, and then stirred at 240 rpm for 4 minutes to obtain a high-strength and durable grout.

[0044] Comparative Example 1 This comparative example provides a high-strength and durable grouting material, whose composition and preparation method are similar to those of Example 1, except that the hydroxy fatty acids and nano-oxides are not prepared as a composite but are added separately to the grouting material. The preparation method includes the following steps: Sulfoaluminate cement, silicate cement, silica fume, amorphous aluminosilicate microspheres, quartz sand and lightly calcined MgO were mixed and stirred at 60 rpm for 2 min to obtain the first mixture; The first mixture was mixed with hydroxy fatty acid (fumaric acid-monoepoxide ester), nano oxide (nano ZnO), and 4,4′-oxobisbenzenesulfonyl hydrazine, and stirred at 120 rpm for 1.5 min to obtain a dry material. Polycarboxylate superplasticizer, defoamer and water are mixed evenly to obtain a liquid phase; The liquid phase and dry material are mixed, stirred at 60 rpm for 30 seconds, and then stirred at 240 rpm for 4 minutes to obtain a high-strength and durable grout.

[0045] The remaining conditions are the same as in Example 1, and will not be repeated here.

[0046] Comparative Example 2 This comparative example provides a high-strength, durable grouting material, whose composition and preparation method are similar to those of Example 1, except that hydroxy fatty acid nano-oxides are not added. Specifically, by weight, the raw materials are 610 parts of sulfoaluminate cement, 90 parts of silicate cement, 105 parts of silica fume, 55 parts of amorphous aluminosilicate microspheres, 1.2 parts of 4,4′-oxobisbenzenesulfonyl hydrazine, 20 parts of lightly calcined MgO, 1040 parts of quartz sand, 21 parts of polycarboxylate superplasticizer, 0.18 parts of defoamer, and 157 parts of water. All other conditions are the same as in Example 1 and will not be repeated.

[0047] Comparative Example 3 This comparative example provides a high-strength, durable grouting material, prepared using a method similar to that of Example 1, except that amorphous aluminosilicate microspheres are replaced with an equal mass of metakaolin. Specifically, by mass, the raw materials are: 610 parts sulfoaluminate cement, 90 parts silicate cement, 105 parts silica fume, 55 parts metakaolin, 3.0 parts hydroxy fatty acid nano-oxide, 1.2 parts 4,4′-oxobisbenzenesulfonyl hydrazine, 20 parts lightly calcined MgO, 1040 parts quartz sand, 21 parts polycarboxylate superplasticizer, 0.18 parts defoamer, and 157 parts water. All other conditions are the same as in Example 1 and will not be repeated.

[0048] Comparative Example 4 This comparative example provides a high-strength, durable grouting material, prepared using a method similar to that of Example 1, except that amorphous aluminosilicate microspheres are not added. Specifically, by weight, the raw materials are: 610 parts sulfoaluminate cement, 90 parts silicate cement, 105 parts silica fume, 3.0 parts hydroxy fatty acid nano-oxide, 1.2 parts 4,4′-oxobisbenzenesulfonyl hydrazine, 20 parts lightly calcined MgO, 1040 parts quartz sand, 21 parts polycarboxylate superplasticizer, 0.18 parts defoamer, and 157 parts water. All other conditions are the same as in Example 1 and will not be repeated.

[0049] Comparative Example 5 This comparative example provides a high-strength, durable grouting material, the preparation method of which is similar to that of Example 1, except that 4,4′-oxobisbenzenesulfonyl hydrazine is replaced with an equal mass of aluminum powder. Specifically, by mass, the raw materials are 610 parts of sulfoaluminate cement, 90 parts of silicate cement, 105 parts of silica fume, 55 parts of amorphous aluminosilicate microspheres, 3.0 parts of hydroxy fatty acid-nano oxides, 1.2 parts of aluminum powder, 20 parts of lightly calcined MgO, 1040 parts of quartz sand, 21 parts of polycarboxylate superplasticizer, 0.18 parts of defoamer, and 157 parts of water. All other conditions are the same as in Example 1 and will not be repeated.

[0050] Verification test The high-strength, durable grouts prepared in Examples 1-4 and Comparative Examples 1-5 were subjected to performance tests. Flowability and 30-minute retention rate were tested according to GB / T 50448-2015. Compressive strength and flexural strength were tested according to GB / T 17671-1999. Self-shrinkage properties were determined according to GB / T 51039-2014. Drying shrinkage was determined according to GB / T 29417-2012. Electrical flux was determined according to GB / T 50082-2009. Freezing resistance was determined according to GB / T 50082-2009. Sulfate resistance was determined according to GB / T 50082-2009. The test results are shown in Tables 1 and 2.

[0051] Table 1. Test results of workability and mechanical properties of high-strength durable grout.

[0052] Table 2. Test results of volume stability and durability of high-strength durable grout.

[0053] As shown in Tables 1 and 2, the high-strength grouting materials prepared in Examples 1 to 4 of this invention are significantly superior to the comparative examples in terms of workability, mechanical properties, volume stability, and durability. Compared with Example 1, the comparative examples, after destroying the structure or compatibility of key components, lead to a greater loss of fluidity and a significant decrease in strength. In terms of volume stability and durability, all comparative examples exhibit problems such as increased shrinkage, increased permeability, and a significant deterioration in freeze-thaw resistance and corrosion resistance. In particular, the freeze-thaw resistance grades of comparative examples 3 and 5 are less than F160, making it difficult to meet the requirements of cold weather or marine engineering.

[0054] In summary, the high-strength and durable grouting material of the present invention can only achieve ultra-high strength, low shrinkage, ultra-low permeability and excellent freeze-thaw resistance when the hydroxy fatty acid nano-oxide is introduced in a pre-composite form, amorphous aluminosilicate microspheres are used as functional carriers, and 4,4′-oxobisbenzenesulfonyl hydrazine is used as a low-temperature gas generating agent.

[0055] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-strength, durable grouting material, characterized in that: Including cement, hydroxy fatty acid nano-oxides, and amorphous aluminosilicate microspheres; The hydroxy fatty acids in the hydroxy fatty acid nano-oxide include one or more of ricinoleic acid, thiolactic acid, or 12-hydroxystearic acid. The hydroxy fatty acid nano-oxides include one or more of nano-ZnO, nano-MgO, nano-CaO, nano-Al2O3, nano-TiO2, or nano-ZrO2.

2. The high-strength, durable grouting material as described in claim 1, characterized in that: The mass ratio of nano-oxide to hydroxy fatty acid in the hydroxy fatty acid-nano-oxide is 1:1.2~2.

0.

3. The high-strength, durable grouting material as described in claim 1, characterized in that: The preparation method of the hydroxy fatty acid-nano oxide includes the following steps: dissolving hydroxy fatty acid in an organic solvent, adding nano oxide, and shearing to obtain hydroxy fatty acid-nano oxide.

4. The high-strength, durable grouting material as described in claim 1, characterized in that: The method for preparing the amorphous aluminosilicate microspheres includes the following steps: The metakaolin suspension was mixed with silica sol and sodium aluminate solution to obtain a homogenate; After homogenization and granulation, the amorphous aluminosilicate microspheres were obtained by calcination.

5. The high-strength, durable grouting material as described in claim 4, characterized in that: Based on the mass of metakaolin, the mass ratio of the metakaolin suspension to silica sol and sodium aluminate solution is 100:100~200:50~125; the particle size of the amorphous aluminosilicate microspheres is 5~8μm.

6. The high-strength, durable grouting material as described in claim 4, characterized in that: The calcination temperature is 620℃~675℃, and the duration is 1.5~2.5h.

7. The high-strength, durable grouting material as described in claim 5, characterized in that: The mass concentration of the metakaolin suspension is 30% to 50%; the solid content of the homogenate is 30% to 45%.

8. The high-strength, durable grouting material as described in claim 1, characterized in that: By weight, the high-strength durable grout comprises 590-630 parts of sulfoaluminate cement, 70-110 parts of silicate cement, 95-115 parts of silica fume, 45-65 parts of amorphous aluminosilicate microspheres, 2.2-3.8 parts of hydroxy fatty acid nano-oxide, 0.8-1.5 parts of 4,4′-oxobisbenzenesulfonyl hydrazine, 15-25 parts of lightly calcined MgO, 1010-1070 parts of quartz sand, 19-23 parts of polycarboxylate superplasticizer, 0.1-0.25 parts of defoamer, and 152-162 parts of water.

9. The method for preparing the high-strength and durable grouting material according to any one of claims 1 to 8, characterized in that: Includes the following steps: Sulfoaluminate cement, silicate cement, silica fume, amorphous aluminosilicate microspheres, quartz sand, and lightly calcined MgO are mixed to obtain the first mixture; The first mixture was stirred evenly with hydroxy fatty acid nano-oxide and 4,4′-oxobisbenzenesulfonylhydrazine to obtain a dry material. The polycarboxylate superplasticizer, defoamer, and water are mixed evenly to obtain a liquid phase; The liquid phase is mixed with the dry material to obtain a high-strength and durable grout.

10. The application of the high-strength durable grouting material according to any one of claims 1 to 8, or the high-strength durable grouting material prepared by the preparation method of the high-strength durable grouting material according to claim 9, in operations in extremely cold or highly permeable environments.

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