Anti-erosion hydraulic concrete and preparation method thereof

Abstract

The invention provides anti-erosion hydraulic concrete and a preparation method thereof, and belongs to the technical field of concrete. The concrete comprises the following components: composite cement, high-activity nano-modified metakaolin, blast furnace slag powder, low-calcium fly ash, coarse aggregate, natural river sand fine aggregate, granite machine-made sand fine aggregate, an erosion inhibitor, a functional additive, an early-strength polycarboxylic high-performance water reducer, a composite air entraining agent and the like. The composite cement comprises sulphoaluminate cement, Portland cement and polymer waterproof mortar. The high-activity nano modified metakaolin is obtained by modifying metakaolin with an organic silicon-ZnO composite emulsion and then drying. The erosion inhibitor comprises organic carboxylate, a hydrophobic-crystallization complexing agent and a pH buffer type corrosion inhibitor. The functional auxiliary agent comprises an itaconic acid and acrylic acid copolymer, a JRY-F concrete waterproof agent and polyethylene glycol-400 dilaurate. The composite air entraining agent comprises liquid sodium abietate and sodium alpha-olefin sulfonate. Through component synergism, modification and grading, an anti-erosion barrier is constructed.

Description

Technical Field

[0001] This invention belongs to the field of concrete technology, specifically relating to an anti-erosion hydraulic concrete and its preparation method. Background Technology

[0002] Hydraulic concrete, as a core material in water conservancy engineering construction, bears the heavy responsibility of constructing various hydraulic structures, such as dams, sluices, and water pipelines. It plays a crucial role in the rational utilization of water resources, flood control, irrigation, and power generation. Its development history is closely linked to the progress of water conservancy, with continuous technological innovation and gradual performance optimization.

[0003] Early hydraulic concrete had a relatively simple composition, mainly consisting of cement, aggregates, and water. However, with the continuous expansion of hydraulic engineering projects and the increasing demands for durability, this simple concrete quickly revealed numerous problems. For example, in environments with prolonged contact with water, its impermeability was insufficient, allowing moisture to easily penetrate the concrete, leading to steel corrosion and structural loosening. In cold regions, its poor frost resistance caused severe damage to the internal structure under freeze-thaw cycles, significantly shortening the service life of hydraulic structures. To address these issues, admixtures such as water-reducing agents and air-entraining agents began to be widely used in hydraulic concrete. Furthermore, mineral admixtures such as fly ash and slag powder gradually became important components of hydraulic concrete.

[0004] With the continuous advancement of materials science and engineering technology, high-performance hydraulic concrete has emerged. This type of concrete, through optimized mix design and the use of high-quality raw materials, further enhances its overall performance. For example, by adjusting the aggregate gradation, the concrete achieves higher density; the use of high-performance water-reducing agents results in a lower water-cement ratio, thereby improving the concrete's strength and durability. Simultaneously, new admixtures and additives are constantly emerging, such as silica fume, which possesses extremely high pozzolanic activity, capable of filling the pores within the concrete, enhancing the bond between cement paste and aggregates, and significantly improving the concrete's impermeability and erosion resistance.

[0005] Despite significant technological advancements in hydraulic concrete, its corrosion resistance remains a challenge in practical applications and requires further improvement. Hydraulic concrete operates in complex aquatic environments, exposed to various corrosive media. Besides common sulfate attack, it can also be affected by acids, alkalis, seawater, and microorganisms, impacting its service life and safety.

[0006] To improve the erosion resistance of hydraulic concrete, a multi-pronged approach is needed. In materials research and development, continued exploration of new admixtures and additives is necessary to optimize the microstructure of concrete and enhance its erosion resistance. In mix design, precise adjustments to the water-cement ratio, aggregate gradation, and admixture dosage are crucial for optimizing concrete performance and meeting the ever-increasing demands of hydraulic concrete applications. Summary of the Invention

[0007] To address the need for improvement in the erosion resistance of existing hydraulic concrete to meet the ever-increasing demands of its applications, this invention provides an erosion-resistant hydraulic concrete and its preparation method. The concrete is prepared by combining specially formulated composite cement, highly active nano-modified metakaolin, erosion inhibitors, functional additives, and composite air-entraining agents with coarse and fine aggregates of a specific gradation. By optimizing the cementitious system and aggregate gradation, a highly dense structure is formed, physically blocking the penetration pathways of corrosive media such as moisture, sulfates, and chloride ions. Functional additives chemically inhibit erosion reactions. Simultaneously, synergistic hydration reactions balance early and late-stage strength with freeze-thaw resistance and shrinkage resistance, overcoming the durability shortcomings of traditional hydraulic concrete caused by its loose structure and insufficient impermeability. Through the design of synergistic components, modification, and particle size distribution, a multi-layered erosion-resistant barrier is constructed. The specific technical solution is as follows: An anti-erosion hydraulic concrete comprises the following raw materials in parts by weight: 200-220 parts composite cement, 30-40 parts highly active nano-modified metakaolin, 80-100 parts blast furnace slag powder, 70-80 parts low-calcium fly ash, 1050-1100 parts coarse aggregate, 650-700 parts natural river sand fine aggregate, 80-100 parts granite manufactured sand fine aggregate, 10-15 parts erosion inhibitor, 10-15 parts functional additives, 5-7 parts early-strength polycarboxylic acid high-performance water-reducing agent, 0.06-0.09 parts composite air-entraining agent, and 135-150 parts water; The composite cement is made of sulfoaluminate cement, silicate cement and polymer waterproof mortar in a mass ratio of 1:(1.4~1.6):(0.2~0.3); The highly active nano-modified metakaolin is obtained by drying metakaolin after modification with an organosilicon-ZnO composite emulsion; the organosilicon-ZnO composite emulsion is formulated with water, polyether-modified organosilicon emulsion, KH-570 silane coupling agent and nano ZnO. The coarse aggregate is composed of basalt crushed stone and granite crushed stone in a mass ratio of 1:(1~1.5); The corrosion inhibitor is composed of an organic carboxylate, a hydrophobic-crystallizing composite agent, and a pH-buffered corrosion inhibitor in a mass ratio of (1.0–1.5):(3.0–4.5):(1.7–2.4); the organic carboxylate is composed of sodium citrate and potassium tartrate in a mass ratio of (2–2.5):(1–1.2); the hydrophobic-crystallizing composite agent is composed of hydrophobic nano-silica and crystalline active component CaSiO3 in a mass ratio of 1:(1–1.5); the pH-buffered corrosion inhibitor is composed of sodium molybdate and cyclohexylamine in a mass ratio of (4–5):1. The functional additive is composed of itaconic acid acrylic copolymer, JRY-F concrete waterproofing agent and polyethylene glycol-400 dilaurate in a mass ratio of 3:(1-1.5):(0.6-0.8). The composite air-entraining agent is made by mixing liquid sodium rosinate and sodium α-olefin sulfonate in a mass ratio of 5:(1 to 1.5).

[0008] The preparation method of the highly active nano-modified metakaolin in the above concrete includes: mixing metakaolin with organosilicon-ZnO composite emulsion evenly, drying, and air-jet pulverizing to a D50 of less than 3μm to obtain highly active nano-modified metakaolin.

[0009] In the above-mentioned method for preparing highly active nano-modified metakaolin, the particle size of the metakaolin is sieved through a 650-800 mesh sieve; the amount of the organosilicon-ZnO composite emulsion is 15%-20% of the mass of the metakaolin; the organosilicon-ZnO composite emulsion is prepared by mixing water, polyether-modified organosilicon emulsion, KH-570 silane coupling agent and nano-ZnO in a mass ratio of 10:(3-5):(0.5-0.8):(1.5-2), and adjusting the pH to 8.3-8.8; the solid content of the polyether-modified organosilicon emulsion is 60wt%-65wt%; and the drying temperature is 60℃-65℃.

[0010] In the above-mentioned concrete, the D50 of the blast furnace slag powder is less than 10 μm.

[0011] In the above-mentioned concrete, the low-calcium fly ash has a D50 of less than 50 μm and a CaO content of less than 5 wt%.

[0012] In the above concrete, the continuous gradation of the coarse aggregate is as follows: 5mm ≤ particle size < 10mm accounts for 30wt% to 35wt%, 10 ≤ particle size < 18mm accounts for 35wt% to 40wt%, and 18 ≤ particle size < 25mm accounts for 25wt% to 30wt%.

[0013] In the above-mentioned concrete, the discontinuous gradation of the natural river sand fine aggregate is as follows: 35wt% to 40wt% in the 40-50 mesh range, 45wt% to 50wt% in the 60-80 mesh range, and 15wt% to 20wt% in the 100-120 mesh range.

[0014] In the above concrete, the discontinuous gradation of the granite manufactured sand fine aggregate is as follows: 60wt% to 70wt% of the 50-70 mesh range and 30wt% to 40wt% of the 100-150 mesh range.

[0015] In the above-mentioned concrete, the water content is specified as follows: chloride ion content <200mg / L, sulfate ion content <600mg / L.

[0016] The above-mentioned method for preparing erosion-resistant hydraulic concrete includes the following steps: S1: Mix composite cement, blast furnace slag powder and low-calcium fly ash according to the mass fraction to obtain the mixture; S2: Mix coarse aggregate, natural river sand fine aggregate, and granite manufactured sand fine aggregate according to the mass fraction; then add 70wt%~80wt% water, early-strength polycarboxylic acid high-performance water-reducing agent and composite air-entraining agent, and mix; then add the mixture, highly active nano-modified metakaolin, erosion inhibitor and functional additives, and mix; finally add the remaining water, mix, and obtain concrete.

[0017] The present invention provides an anti-erosion hydraulic concrete and its preparation method, the beneficial effects of which include: I. The anti-erosion hydraulic concrete of this invention forms a highly dense structure by optimizing the cementitious system and aggregate gradation, which blocks the penetration path of corrosive media such as water, sulfate, and chloride ions at the physical level; it inhibits the erosion reaction at the chemical level with the help of functional additives; at the same time, it balances early and late strength and antifreeze and anti-shrinkage performance through synergistic hydration reaction, which solves the durability shortcomings of traditional hydraulic concrete caused by loose structure and insufficient impermeability. Through the design of synergistic components, modification and particle size distribution, a multi-layered anti-erosion barrier is constructed.

[0018] II. Composite cement is made by blending sulfoaluminate cement, silicate cement and polymer waterproof mortar in a specific ratio. Sulfoaluminate cement hydrates quickly, has high early strength and low Ca(OH)2 content in hydration products, while silicate cement provides support for later strength. The two work together to form a double gel structure, taking into account both early and late strength. The polymer waterproof mortar fills the capillary pores and microcracks inside the cement stone, forming a continuous hydrophobic system, blocking the penetration path of corrosive media, and improving the interfacial bonding between cement and aggregate, reducing interfacial porosity.

[0019] III. Highly Active Nano-Modified Metakaolin: After modification with an organosilicon-ZnO composite emulsion, the organosilicon segments form a hydrophobic film to prevent particle agglomeration, while nano-ZnO fills the micropores. Combined with the ultrafine particle size (D50 < 3 μm) after air-jet milling, this significantly improves the compactness of concrete and enhances its impermeability and erosion resistance. Blast furnace slag powder (D50 < 10 μm) participates in the later hydration reaction, supplementing the generation of CSH gel and enhancing the structural stability of concrete. Low-calcium fly ash (D50 < 50 μm, CaO < 5 wt%) fills the voids in the cementitious system through optimized particle size distribution, reducing porosity and increasing density.

[0020] Fourth, the coarse aggregate is a mixture of basalt crushed stone and granite crushed stone in a specific ratio, and a continuous gradation is designed. By using different particle sizes to complement each other, the voids are reduced and the supporting effect of the skeleton is enhanced.

[0021] 5. Fine aggregate is made by blending natural river sand and manufactured granite sand in a specific ratio and designing a discontinuous gradation: the river sand is mainly 40-50 mesh and 60-80 mesh, and the manufactured sand is mainly 50-70 mesh. The complementary particle size of the two achieves continuous filling of "coarse-medium-fine", reducing the porosity of fine aggregate. At the same time, the angular structure of the manufactured granite sand enhances the interlocking effect with cement paste and improves the interface transition zone.

[0022] VI. Erosion Inhibitor: Organic carboxylate (sodium citrate + potassium tartrate) chelates free Ca2+ 2+ The process reduces the amount of raw materials for sulfate reactions; the hydrophobic-crystallization composite agent (hydrophobic nano-SiO2 + CaSiO3) forms a hydrophobic layer and generates calcium silicate crystals to block micropores; the pH buffering corrosion inhibitor (sodium molybdate + cyclohexylamine) stabilizes the internal environment and synergistically inhibits the corrosion reaction.

[0023] VII. Functional Additives: Itaconic acid-acrylic acid copolymer disperses gel particles through electrostatic repulsion, preventing agglomeration; JRY-F waterproofing agent enhances impermeability; polyethylene glycol-400 dilaurate retains water (reduces drying cracks) and plasticizes (improves compaction).

[0024] 8. Composite air-entraining agent (liquid sodium rosinate + sodium α-alkenyl sulfonate): Sodium α-alkenyl sulfonate efficiently introduces microbubbles, while liquid sodium rosinate stabilizes the bubble film. The bubbles absorb expansion stress during freeze-thaw cycles, thus improving freeze resistance.

[0025] 9. Preparation steps: Mix in stages (first aggregate with some water and water-reducing agent, then add cementitious materials, etc.) to ensure uniform material dispersion; control the mixing speed and time to avoid excessive stirring that may cause bubbles to escape or particles to agglomerate.

[0026] 10. The various components of concrete achieve a leap in performance through the three-dimensional synergy of "structure-function-response": (1) Structural synergy: The double gel structure of composite cement and the ultrafine particles of mineral admixtures (meta-kaolin, slag powder, fly ash) form a dense matrix. Combined with aggregate gradation optimization (continuous gradation + discontinuous gradation), the porosity is reduced from macro to micro, providing a physical basis for erosion resistance.

[0027] (2) Functional synergy: The "chelation-hydrophobic-buffering" function of the erosion inhibitor is superimposed with the "hydrophobic-filling" effect of the highly active nano-modified metakaolin, which not only blocks the penetration of the erosion medium, but also inhibits its reaction with cement hydration products; the "water retention-foam stabilization" synergy of the composite air-entraining agent and functional additives improves the freeze resistance while reducing drying shrinkage.

[0028] (3) Synergistic reaction: The early hydration of sulfoaluminate cement complements the later hydration of silicate cement and slag powder, avoiding strength development gaps; the polymer waterproof mortar and aggregate interface optimization synergize to reduce interface transition zone defects, enhance overall structural stability, and enable concrete to achieve better results in strength, impermeability, and erosion resistance. Detailed Implementation

[0029] The present invention will be further described below with reference to specific implementation examples, but the present invention is not limited to these embodiments.

[0030] Example 1 An anti-erosion hydraulic concrete comprises the following raw materials in parts by weight: 200 parts composite cement, 30 parts highly active nano-modified metakaolin, 80 parts blast furnace slag powder, 70 parts low-calcium fly ash, 1050 parts coarse aggregate, 650 parts natural river sand fine aggregate, 80 parts granite manufactured sand fine aggregate, 10 parts erosion inhibitor, 10 parts functional additives, 5 parts early-strength polycarboxylic acid high-performance water-reducing agent, 0.06 parts composite air-entraining agent, and 135 parts water.

[0031] Composite cement is made by mixing sulfoaluminate cement, silicate cement and polymer waterproof mortar in a mass ratio of 1:1.5:0.25.

[0032] The preparation method of highly active nano-modified metakaolin includes: mixing water, polyether-modified organosilicon emulsion, KH-570 silane coupling agent and nano ZnO in a mass ratio of 10:3:0.5:1.5, adjusting the pH to 8.3 to obtain organosilicon-ZnO composite emulsion; passing metakaolin through a 650-mesh sieve; spraying 15% by weight of organosilicon-ZnO composite emulsion into the stirred metakaolin, mixing evenly, drying at 60℃ to constant weight, and air-jet pulverizing to a D50 of less than 3μm to obtain highly active nano-modified metakaolin.

[0033] The D50 of blast furnace slag powder is below 10μm. The D50 of low-calcium fly ash is below 50μm, and the CaO content is 3.6wt%.

[0034] The coarse aggregate is composed of basalt crushed stone and granite crushed stone in a 1:1 mass ratio. The continuous gradation of the coarse aggregate is as follows: 30 wt% for particles 5 mm ≤ < 10 mm, 40 wt% for particles 10 ≤ < 18 mm, and 30 wt% for particles 18 ≤ < 25 mm. The discontinuous gradation of the natural river sand fine aggregate is as follows: 35 wt% for particles in the 40-50 mesh range, 50 wt% for particles in the 60-80 mesh range, and 15 wt% for particles in the 100-120 mesh range, with a mud content of 2.8 wt%. The discontinuous gradation of the granite manufactured sand fine aggregate is as follows: 65 wt% for particles in the 50-70 mesh range and 35 wt% for particles in the 100-150 mesh range.

[0035] The corrosion inhibitor is composed of an organic carboxylate, a hydrophobic-crystallizing composite agent, and a pH-buffered corrosion inhibitor in a mass ratio of 1.0:3.0:1.7. Specifically, the organic carboxylate is composed of sodium citrate and potassium tartrate in a mass ratio of 2:1; the hydrophobic-crystallizing composite agent is composed of hydrophobic nano-silica and the crystalline active component CaSiO3 in a mass ratio of 1:1; and the pH-buffered corrosion inhibitor is composed of sodium molybdate and cyclohexylamine in a mass ratio of 4:1.

[0036] The functional additives are formulated from itaconic acid acrylic copolymer, JRY-F concrete waterproofing agent and polyethylene glycol-400 bislaurate in a mass ratio of 3:1:0.6.

[0037] The composite air-entraining agent is made of liquid sodium rosinate and sodium α-olefin sulfonate in a mass ratio of 5:1.

[0038] The water specifications are: chloride ion content 170 mg / L, sulfate ion content 385 mg / L.

[0039] The above-mentioned method for preparing erosion-resistant hydraulic concrete includes the following steps: S1: According to the mass fractions, the composite cement, blast furnace slag powder and low calcium fly ash are mixed at 30 rpm for 2 minutes to obtain the mixture; S2: According to the mass fraction, mix the coarse aggregate, natural river sand fine aggregate, and granite manufactured sand fine aggregate at 15 rpm for 2 min; then add 70 wt% water, early-strength polycarboxylic acid high-performance water-reducing agent and composite air-entraining agent, and mix at 35 rpm for 3 min; then add the mixture, highly active nano-modified metakaolin, erosion inhibitor and functional additives, and mix at 35 rpm for 2 min; finally add the remaining water and mix at 35 rpm for 1 min to obtain concrete.

[0040] Example 2 An anti-erosion hydraulic concrete comprises the following raw materials in parts by weight: 210 parts composite cement, 35 parts highly active nano-modified metakaolin, 90 parts blast furnace slag powder, 75 parts low-calcium fly ash, 1080 parts coarse aggregate, 675 parts natural river sand fine aggregate, 90 parts granite manufactured sand fine aggregate, 13 parts erosion inhibitor, 12 parts functional additives, 6 parts early-strength polycarboxylic acid high-performance water-reducing agent, 0.07 parts composite air-entraining agent, and 142 parts water.

[0041] Composite cement is made by mixing sulfoaluminate cement, silicate cement and polymer waterproof mortar in a mass ratio of 1:1.4:0.2.

[0042] The preparation method of highly active nano-modified metakaolin includes: mixing water, polyether-modified organosilicon emulsion, KH-570 silane coupling agent and nano ZnO in a mass ratio of 10:4:0.7:1.8, adjusting the pH to 8.5 to obtain organosilicon-ZnO composite emulsion; passing metakaolin through an 800-mesh sieve; spraying 18% by weight of organosilicon-ZnO composite emulsion into the stirred metakaolin, mixing evenly, drying at 62℃ to constant weight, and air-jet pulverizing to a D50 of less than 3μm to obtain highly active nano-modified metakaolin.

[0043] The D50 of blast furnace slag powder is below 10μm. The D50 of low-calcium fly ash is below 50μm, and the CaO content is 4.2wt%.

[0044] The coarse aggregate is composed of basalt crushed stone and granite crushed stone in a mass ratio of 1:1.2. The continuous gradation of the coarse aggregate is as follows: 35 wt% for particles 5 mm ≤ < 10 mm, 35 wt% for particles 10 ≤ < 18 mm, and 30 wt% for particles 18 ≤ < 25 mm. The discontinuous gradation of the natural river sand fine aggregate is as follows: 40 wt% for particles in the 40-50 mesh range, 45 wt% for particles in the 60-80 mesh range, and 15 wt% for particles in the 100-120 mesh range, with a mud content of 2.2 wt%. The discontinuous gradation of the granite manufactured sand fine aggregate is as follows: 60 wt% for particles in the 50-70 mesh range and 40 wt% for particles in the 100-150 mesh range.

[0045] The corrosion inhibitor is composed of an organic carboxylate, a hydrophobic-crystallizing composite agent, and a pH-buffered corrosion inhibitor in a mass ratio of 1.3:3.8:2.0. Specifically, the organic carboxylate is composed of sodium citrate and potassium tartrate in a mass ratio of 2.3:1.1; the hydrophobic-crystallizing composite agent is composed of hydrophobic nano-silica and the crystalline active component CaSiO3 in a mass ratio of 1:1.2; and the pH-buffered corrosion inhibitor is composed of sodium molybdate and cyclohexylamine in a mass ratio of 4.5:1.

[0046] The functional additives are formulated from itaconic acid acrylic copolymer, JRY-F concrete waterproofing agent and polyethylene glycol-400 bislaurate in a mass ratio of 3:1.3:0.7.

[0047] The composite air-entraining agent is made by mixing liquid sodium rosinate and sodium α-olefin sulfonate in a mass ratio of 5:1.2.

[0048] The water specifications are: chloride ion content 154 mg / L, sulfate ion content 526 mg / L.

[0049] The above-mentioned method for preparing erosion-resistant hydraulic concrete includes the following steps: S1: According to the mass fractions, the composite cement, blast furnace slag powder and low calcium fly ash are mixed at 32 rpm for 1.5 min to obtain the mixture; S2: According to the mass fraction, mix the coarse aggregate, natural river sand fine aggregate, and granite manufactured sand fine aggregate at 18 rpm for 1.5 min; then add 75 wt% water, early-strength polycarboxylic acid high-performance water-reducing agent and composite air-entraining agent, and mix at 32 rpm for 4 min; then add the mixture, highly active nano-modified metakaolin, erosion inhibitor and functional additives, and mix at 32 rpm for 2.5 min; finally add the remaining water and mix at 32 rpm for 1.5 min to obtain concrete.

[0050] Example 3 An anti-erosion hydraulic concrete comprises the following raw materials in parts by weight: 220 parts composite cement, 40 parts highly active nano-modified metakaolin, 100 parts blast furnace slag powder, 80 parts low-calcium fly ash, 1100 parts coarse aggregate, 700 parts natural river sand fine aggregate, 100 parts granite manufactured sand fine aggregate, 15 parts erosion inhibitor, 15 parts functional additives, 7 parts early-strength polycarboxylic acid high-performance water-reducing agent, 0.09 parts composite air-entraining agent, and 150 parts water.

[0051] Composite cement is made by mixing sulfoaluminate cement, silicate cement and polymer waterproof mortar in a mass ratio of 1:1.6:0.3.

[0052] The preparation method of highly active nano-modified metakaolin includes: mixing water, polyether-modified organosilicon emulsion, KH-570 silane coupling agent and nano ZnO in a mass ratio of 10:5:0.8:2, adjusting the pH to 8.8 to obtain organosilicon-ZnO composite emulsion; passing metakaolin through an 800-mesh sieve; spraying 20% ​​by weight of organosilicon-ZnO composite emulsion into the stirred metakaolin, mixing evenly, drying at 65℃ to constant weight, and air-jet pulverizing to a D50 of less than 3μm to obtain highly active nano-modified metakaolin.

[0053] The D50 of blast furnace slag powder is below 10μm. The D50 of low-calcium fly ash is below 50μm, and the CaO content is 4.5wt%.

[0054] The coarse aggregate is composed of basalt crushed stone and granite crushed stone in a mass ratio of 1:1.5. The continuous gradation of the coarse aggregate is as follows: 35 wt% for particles 5 mm ≤ < 10 mm, 40 wt% for particles 10 ≤ < 18 mm, and 25 wt% for particles 18 ≤ < 25 mm. The discontinuous gradation of the natural river sand fine aggregate is as follows: 35 wt% for particles in the 40-50 mesh range, 45 wt% for particles in the 60-80 mesh range, and 20 wt% for particles in the 100-120 mesh range, with a mud content of 2.5 wt%. The discontinuous gradation of the granite manufactured sand fine aggregate is as follows: 70 wt% for particles in the 50-70 mesh range and 30 wt% for particles in the 100-150 mesh range.

[0055] The corrosion inhibitor is composed of an organic carboxylate, a hydrophobic-crystallizing composite agent, and a pH-buffered corrosion inhibitor in a mass ratio of 1.5:4.5:2.4. Specifically, the organic carboxylate is composed of sodium citrate and potassium tartrate in a mass ratio of 2.5:1.2; the hydrophobic-crystallizing composite agent is composed of hydrophobic nano-silica and the crystalline active component CaSiO3 in a mass ratio of 1:1.5; and the pH-buffered corrosion inhibitor is composed of sodium molybdate and cyclohexylamine in a mass ratio of 5:1.

[0056] The functional additives are formulated from itaconic acid acrylic copolymer, JRY-F concrete waterproofing agent and polyethylene glycol-400 bislaurate in a mass ratio of 3:1.5:0.8.

[0057] The composite air-entraining agent is made by mixing liquid sodium rosinate and sodium α-olefin sulfonate in a mass ratio of 5:1.5.

[0058] The water specifications are: chloride ion content 125 mg / L, sulfate ion content 438 mg / L.

[0059] The above-mentioned method for preparing erosion-resistant hydraulic concrete includes the following steps: S1: According to the mass fractions, the composite cement, blast furnace slag powder and low calcium fly ash are mixed at 35 rpm for 1 min to obtain the mixture; S2: According to the mass fraction, mix the coarse aggregate, natural river sand fine aggregate, and granite manufactured sand fine aggregate at 20 rpm for 1 min; then add 80 wt% water, early-strength polycarboxylic acid high-performance water-reducing agent and composite air-entraining agent, and mix at 30 rpm for 5 min; then add the mixture, highly active nano-modified metakaolin, erosion inhibitor and functional additives, and mix at 30 rpm for 3 min; finally add the remaining water and mix at 30 rpm for 2 min to obtain concrete.

[0060] The raw materials used in the above embodiments are sourced as follows: Sulfoaluminate cement is from Wuxi Jingpeng New Building Materials Co., Ltd., and is low-alkali. Silicate cement is from Ningguo Cement Plant of Anhui Conch Cement Co., Ltd., and is P.II52.5R silicate cement. Polymer waterproof mortar is from Wuxi Jingpeng New Building Materials Co., Ltd., and is a cement-based solid material. Polyether-modified silicone emulsion is from Dongguan Haoyouduo New Materials Co., Ltd., product number D-001, with a solid content adjusted to 60wt%~65wt%. KH-570 silane coupling agent is from Dongguan Kangjin New Materials Technology Co., Ltd. Nano ZnO is from Hangzhou Jiupeng New Materials Co., Ltd., model J50, specification 50nm grade. Metakaolin is from Guangzhou Changyu Chemical Co., Ltd., and is the undersize material after sieving using a 650-800 mesh sieve. Blast furnace slag powder is from Lingshou County Yaoxin Mineral Products Processing Plant, and is S95 mineral powder. Low-calcium fly ash is from Shijiazhuang Xuhan New Materials Technology Co., Ltd. Sodium citrate is from Suzhou Yueda Chemical Co., Ltd. Potassium tartrate is sourced from Henan Chengshuo New Material Technology Co., Ltd. Hydrophobic nano-silica is sourced from Jiangsu Tianxing New Material Co., Ltd., model TSP-L12, specification 20nm grade. The crystalline active component CaSiO3 is sourced from Jinan Zhiheng Zhiyuan Chemical Technology Co., Ltd., anhydrous calcium sulfate. Sodium molybdate is sourced from Henan Zhongjie Chemical Products Co., Ltd. Cyclohexylamine is sourced from Shandong Qiyun Chemical Technology Co., Ltd. Itaconic acid acrylic copolymer is sourced from Changzhou Runyang Chemical Co., Ltd., model GY-318. JRY-F concrete waterproofing agent is sourced from Shanxi Jinrongyuan Building Materials Technology Co., Ltd. Polyethylene glycol-400 dilaurate is sourced from Jiangsu Haian Petrochemical Plant, specification PEG400DL. Early-strength polycarboxylic acid high-performance water-reducing agent is sourced from Shanxi Jinrongyuan Building Materials Technology Co., Ltd., JRY-A polycarboxylic acid high-performance water-reducing agent (early-strength type). Liquid sodium rosinate is sourced from Zhengzhou Chengao Chemical Products Co., Ltd. Sodium α-olefin sulfonate is sourced from China Light Industry Chemical Co., Ltd.

[0061] Comparative Example 1 The difference from Example 1 is that the composite cement is made of sulfoaluminate cement and silicate cement in a mass ratio of 1:1.75, that is, no polymer waterproof mortar is added.

[0062] Comparative Example 2 The difference from Example 1 is that the composite cement is made of silicate cement, sulfoaluminate cement and polymer waterproof mortar in a mass ratio of 1:1.5:0.25, that is, the proportions of sulfoaluminate cement and silicate cement are interchanged.

[0063] Comparative Example 3 The difference from Example 1 is that the highly active nano-modified metakaolin is directly replaced by metakaolin, that is, no highly active nano-modification is performed.

[0064] Comparative Example 4 The difference from Example 1 is that no polyether-modified organosilicon emulsion is added in the preparation of highly active nano-modified metakaolin.

[0065] Comparative Example 5 The difference from Example 1 is that the natural river sand fine aggregate is changed to 730 parts, and the granite manufactured sand fine aggregate is changed to 0 parts.

[0066] Comparative Example 6 The difference from Example 1 is that the discontinuous gradation of the granite manufactured sand fine aggregate is: 35wt% of the 40-50 mesh range, 50wt% of the 60-80 mesh range, and 15wt% of the 100-120 mesh range, which is the same as the gradation of the natural river sand fine aggregate.

[0067] Comparative Example 7 The difference from Example 1 is that: in the corrosion inhibitor, all organic carboxylate salts are sodium citrate; all hydrophobic-crystallizing composite agents are hydrophobic nano-silica; and all pH buffering corrosion inhibitors are sodium molybdate.

[0068] Comparative Example 8 The difference from Example 1 is that no hydrophobic-crystallizing composite agent is added to the erosion inhibitor.

[0069] Comparative Example 9 The difference from Example 1 is that the corrosion inhibitor is made of organic carboxylate, hydrophobic-crystallizing composite agent and pH buffer corrosion inhibitor in a mass ratio of 3.0:1.7:1.0, that is, the ratio is changed.

[0070] Comparative Example 10 The difference from Example 1 is that itaconic acid-acrylic acid copolymer is not added to the functional additives.

[0071] Comparative Example 11 The difference from Example 1 is that polyethylene glycol-400 bislaurate is not added to the functional additives.

[0072] Comparative Example 12 The difference from Example 1 is that the functional additive is made of itaconic acid acrylic copolymer, JRY-F concrete waterproofing agent and polyethylene glycol-400 bislaurate in a mass ratio of 0.6:3:1, that is, the ratio is changed.

[0073] Comparative Example 13 The difference from Example 1 is that the composite air-entraining agent is entirely liquid sodium rosinate.

[0074] Comparative Example 14 The difference from Example 1 is that the composite air-entraining agent is entirely sodium α-olefin sulfonate.

[0075] Comparative Example 15 The difference from Example 1 is that the composite air-entraining agent is made by mixing liquid sodium rosinate and sodium α-alkenyl sulfonate in a mass ratio of 1:5, that is, the ratio is changed.

[0076] The performance of the concrete in the above embodiments and comparative examples was tested as follows: Table 1 Test Items and Parameters

[0077] Sample preparation and curing: Concrete was poured and compacted on a vibrating table (frequency 50Hz, amplitude 0.5mm). The samples were then left to stand for 24 hours in an environment of 20±5℃ and RH≥80% before demolding. Immediately after demolding, the samples were transferred to a standard curing room at 20±2℃ and RH≥95% for curing until the specified age required for testing. Five parallel samples were prepared for each group. The test results are shown in Table 2 below.

[0078] Table 2. Test Results (Values ​​for Parallel Samples)

[0079] The results above show that the concrete in Examples 1 to 3 provides a scientific material ratio and particle size distribution, while also exhibiting good strength, impermeability, and erosion resistance.

[0080] Comparative Example 1 (Composite cement without polymer waterproof mortar): Polymer waterproof mortar can fill the capillary pores and micro-cracks inside cement stone, forming a continuous hydrophobic system that blocks moisture and SO4. 2- Cl - On the one hand, the polymer can penetrate the infiltration pathway of corrosive media; on the other hand, it can penetrate into the interface transition zone between cement and aggregate, improving the interfacial bonding state and reducing interfacial porosity. Without this component, the porosity of cement paste increases significantly, and the number of infiltration channels increases: not only does its impermeability decrease, but corrosive media can also more easily penetrate the interior and react with cement hydration products to form expansive ettringite, leading to increased concrete volume deformation; simultaneously, the bonding force in the interfacial transition zone weakens, the development of compressive strength is hindered, and moisture is more likely to freeze and expand within the pores during freeze-thaw cycles, exacerbating structural damage.

[0081] Comparative Example 2 (Interchange of the proportions of sulfoaluminate cement and silicate cement in composite cement): Sulfoaluminate cement and silicate cement have fundamentally different hydration characteristics. Sulfoaluminate cement hydrates rapidly, forming dense hydrated calcium sulfoaluminate crystals early on, and the Ca(OH)2 content in the hydration products is low. In contrast, the calcium silicate (CSH) hydrated gel formed by silicate cement hydration is less dense and precipitates a large amount of Ca(OH)2. After the proportions were interchanged, the proportion of sulfoaluminate cement decreased: firstly, the early hydration products lacked density, increasing the porosity of the cement stone and weakening its impermeability; secondly, the Ca(OH)2 content increased, becoming SO42-.2- The first is that it provides more reaction sites, which further react with hydrated calcium aluminate to form ettringite, thus exacerbating sulfate erosion and damage; the second is that the hydration exothermic rate slows down, the early strength development lags behind, and the overall structural compactness is delayed.

[0082] Comparative Example 3 (Highly active nano-modified metakaolin replaced with unmodified metakaolin): The performance of the "highly active nano-modified metakaolin" in the examples depends on two modification mechanisms: first, the organosilicon-ZnO composite emulsion forms a hydrophobic film on the surface of metakaolin, reducing its surface energy and preventing aggregation; second, the introduction of nano-ZnO can fill micropores. Unmodified metakaolin lacks the above functions and, without the protection of the hydrophobic film, is prone to aggregation. It not only fails to fill micropores but also forms gaps between aggregates, becoming new channels for corrosive media; furthermore, during freeze-thaw cycles, moisture easily remains in the pores, exacerbating freezing damage.

[0083] Comparative Example 4 (Preparation of Polyether-Modified Organosilicon Emulsion from Highly Active Nano-Modified Metakaolin): The polyether-modified organosilicon emulsion plays three main roles in the modification process: First, as a dispersant, its polyether segments can be adsorbed on the surface of metakaolin particles, preventing particle agglomeration through steric hindrance and ensuring the stability of metakaolin particle size; second, as a hydrophobic modifier, its organosilicon segments can form a continuous hydrophobic layer on the surface of metakaolin, reducing the hydrophilicity of cement paste; and third, as a compatibility regulator, it enhances the interfacial bonding between metakaolin and cement paste, preventing the modified particles from "separating" from the cement paste. Without this component, metakaolin particles undergo severe agglomeration due to their high surface energy. On the one hand, the agglomerates cannot uniformly fill the micropores of the cement stone, instead forming large gaps and increasing the permeation channels. On the other hand, the agglomerated metakaolin cannot fully contact Ca(OH)2, resulting in insufficient reaction, reduced CSH gel formation, and decreased cement stone density. At the same time, the lack of a hydrophobic layer leads to an increase in the water absorption rate of the cement stone, more severe damage from freezing expansion during freeze-thaw cycles, and exacerbated drying shrinkage due to increased porosity.

[0084] Comparative Example 5 (Granite manufactured sand fine aggregate changed to 0 parts, natural river sand increased to 730 parts): There are key differences in particle shape and gradation characteristics between granite manufactured sand and natural river sand. Granite manufactured sand is angular, and in discontinuous gradation, 50-70 mesh coarse particles account for 65%. This not only enhances the mechanical bonding force with cement paste through angular interlocking but also fills the gaps in natural river sand (40-50 mesh accounting for 35%), reducing the overall porosity of fine aggregate. In contrast, natural river sand is round or elliptical, with weak interlocking and a high porosity in its single gradation. Without granite manufactured sand: First, the porosity of fine aggregate increases, requiring more cement paste to fill, resulting in a reduction in effective cementitious materials participating in the cementitious reaction and limiting the development of compressive strength; second, the interlocking effect between aggregate and cement paste weakens, and micro-cracks easily form in the interface transition zone, becoming a weak link for the penetration of corrosive media; third, the gradation continuity of natural river sand is poor, reducing the uniformity of the internal structure of concrete and affecting both impermeability and frost resistance.

[0085] Comparative Example 6 (Granite manufactured sand gradation is the same as natural river sand): The core of the gradation design of "natural river sand + granite manufactured sand" in this example is "complementary filling": natural river sand is mainly composed of medium-sized particles (60-80 mesh), while granite manufactured sand is mainly composed of coarse-sized particles (50-70 mesh). The combination of the two achieves continuous filling of fine aggregate from coarse to fine, minimizing the porosity. After the gradation overlaps, the proportion of coarse-sized particles (50-70 mesh) is insufficient, and the fine aggregate system exhibits the problem of "enrichment of medium-sized particles and lack of coarse-sized particles": on the one hand, the porosity increases, and the cement stone needs more cementitious materials to fill, resulting in a decrease in structural density and a weakening of impermeability; on the other hand, the insufficient proportion of coarse-sized aggregate weakens the "skeleton support" effect between aggregates, hindering the development of compressive strength.

[0086] Comparative Example 7 (Single Component Substitution of Complex Components for Erosion Inhibitors): The function of erosion inhibitors depends on "multi-component synergistic effect", and single substitution disrupts the synergistic mechanism: (1) Sodium citrate (strong Ca 2+ When sodium citrate (with chelating ability) is combined with potassium tartrate (high corrosion inhibition efficiency), it chelates free Ca in concrete. 2+ This reduces the formation of gypsum and ettringite, while potassium tartrate forms an adsorption film on the surface of cement particles, inhibiting the reaction of hydrated calcium aluminate and SO4. 2- The reaction; sodium citrate alone cannot simultaneously achieve "chelation + corrosion inhibition", SO4 2- The reaction rate increases significantly. (2) Hydrophobic nano-silica forms a hydrophobic layer on the cement stone surface, reducing water intrusion, while CaSiO3 (crystallization active component) reacts with cement hydration products to generate fibrous calcium silicate crystals, blocking internal micropores; single hydrophobic nano-silica can only prevent surface water penetration and cannot repair internal pores, so the penetration channels still exist. Single sodium molybdate has poor synergistic film formation and stability with other components.

[0087] Comparative Example 8 (without hydrophobic-crystallizing composite agent in the erosion inhibitor): The hydrophobic-crystallizing composite agent is the core component of the erosion inhibitor for "anti-permeability + pore plugging": hydrophobic nano-silica reduces water adsorption and penetration on the cement stone surface through physical filling and hydrophobic modification; CaSiO3 crystallizes in the micropores and cracks inside the cement stone, and the generated calcium silicate crystals gradually block the penetration channels, forming a "self-healing" effect. Without this component, the erosion inhibitor only retains "chelated Ca 2+ The "pH buffering" function cannot solve the "permeability channel" problem: on the one hand, moisture and corrosive media can still penetrate into the interior through the micropores, and SO4... 2- Cl - The reaction with cement hydration products continues; on the other hand, the internal micropores cannot be blocked by crystallization, and water is easily retained in the pores during freeze-thaw cycles. The expansion of ice leads to increased structural damage, while the compressive strength decreases due to the increase in internal porosity.

[0088] Comparative Example 9 (Change in the Proportion of Erosion Inhibitor Components): The original design logic was "with anti-permeability as the core, supplemented by chelation and pH buffering," with the hydrophobic-crystallizing composite agent having the highest proportion. This prioritized building a "hydrophobic + pore-blocking" anti-permeability barrier to reduce the intrusion of corrosive media. At this point, only a small amount of organic carboxylate and pH-buffered corrosion inhibitor was needed to inhibit the remaining erosion reaction. After the proportion was changed, the proportion of hydrophobic-crystallizing composite agent was insufficient: firstly, the anti-permeability barrier could not be effectively formed, and the intrusion of water and corrosive media increased, far exceeding the chelating capacity of organic carboxylate, leading to SO4... 2- The reaction with cement hydration products is intensified; secondly, the proportion of pH buffering corrosion inhibitors is reduced, making it impossible to stabilize the internal environment of concrete; at the same time, excessive organic carboxylates will slightly inhibit cement hydration, resulting in a reduction in CSH gel formation and hindering the development of compressive strength.

[0089] Comparative Example 10 (functional additives without itaconic acid-acrylic acid copolymer): Itaconic acid-acrylic acid copolymer is the "dispersion core" in the functional additives. Through electrostatic adsorption, it binds to the surface of cementitious material particles such as cement, highly active nano-modified metakaolin, and blast furnace slag powder. Through electrostatic repulsion and steric hindrance, it prevents particle agglomeration, ensuring uniform dispersion of the cementitious materials in the cement paste. Without this component, the cementitious materials are prone to agglomeration: on the one hand, large gaps form between the agglomerates, increasing the porosity of the cement paste, reducing its impermeability, and allowing corrosive media to easily penetrate; on the other hand, uneven dispersion leads to insufficient cement hydration, reducing the amount of CSH gel generated and causing uneven distribution, thus hindering the development of compressive strength; simultaneously, agglomerates accumulate near the aggregate interface, exacerbating the porosity of the interface transition zone, reducing the density of the concrete, and affecting its erosion resistance; in some areas, excessively concentrated hydration can easily generate local shrinkage stress, leading to microcracks and an increase in drying shrinkage.

[0090] Comparative Example 11 (without polyethylene glycol-400 dilaurate in the functional additives): Polyethylene glycol-400 dilaurate is a "water-retaining and plasticizing synergistic component" in the functional additives. Its mechanism of action is twofold: first, as a water-retaining agent, the polyethylene glycol segments (hydrophilic) in the molecule form hydrogen bonds with the free water in the cement paste, slowing down the rate of water evaporation, especially in the initial setting stage after concrete pouring, avoiding "surface drying shrinkage cracks" caused by excessively rapid loss of surface moisture; second, as a plasticizer, its laurate segments (hydrophobic) adsorb onto the surface of cement particles, reducing the friction between particles, improving the workability of concrete, ensuring that air bubbles are fully discharged during vibration, and that aggregates and cement paste are evenly coated, reducing internal pores caused by insufficient compaction. The absence of this component disrupts the "water retention-density balance" of concrete. Insufficient water retention leads to drying defects and reduced impermeability. The lack of plasticizing effect results in insufficient density, increased porosity in the interface transition zone, and the formation of a local loose structure, which in turn reduces compressive strength. Insufficient water retention leads to uneven distribution of moisture inside the concrete, causing stress concentration points for frost heave. Cement stone around air bubbles is prone to cracking, and the freeze-thaw mass loss rate increases.

[0091] Comparative Example 12 (Change in the Proportion of Functional Additive Components): The design logic of the formulation in the previous example was "first ensure uniform dispersion, then enhance waterproofing and water retention." The itaconic acid-acrylic acid copolymer had the highest proportion, ensuring uniform dispersion of the cementitious material and providing a "uniform matrix" for the waterproofing and water-retaining agents. However, the formulation of Comparative Example 12 broke this logic. The core problem was "insufficient dispersion ability, unable to support the effect of excessive waterproofing agent." The proportion of itaconic acid-acrylic acid copolymer was too low, and the cementitious material would still agglomerate, forming a large number of gaps and local loose areas. The waterproofing substance formed in local dense areas, while the uncovered areas remained penetration channels, reducing the impermeability. Excessive JRY-F concrete waterproofing agent would accelerate the cement hydration rate, leading to a concentrated release of early hydration heat, generating temperature stress inside the concrete, easily causing temperature cracks, and hindering the development of compressive strength. Although the proportion of polyethylene glycol-400 dilaurate has increased slightly, the water retention effect cannot be evenly exerted due to the uneven dispersion of cementitious materials. In some areas, the water-retaining agent cannot come into contact with free water due to the obstruction of agglomerates, and the water will still evaporate quickly, forming drying cracks. In some areas, due to excessive water-retaining agent, too much water is retained, and the water is slowly lost in the later stage of concrete hardening, which leads to an increase in drying shrinkage rate.

[0092] Comparative Example 13 (all composite air-entraining agents used liquid sodium rosinate): The function of the composite air-entraining agent relies on a "synergistic mechanism of air entrainment and foam stabilization": α-Alkenyl sulfonate, as an anionic surfactant, has hydrophilic groups (sodium sulfonate) in its molecular structure adsorbed at the cement slurry-air interface, while hydrophobic groups (alkenyl) face the air, rapidly reducing interfacial tension and thus efficiently introducing a large number of microbubbles. Liquid sodium rosinate acts as a "foam stabilizer," with its arisin acid structure forming a tough adsorption film on the bubble surface, enhancing the mechanical strength of the bubble wall and preventing bubbles from merging into large bubbles or escaping during stirring and vibration, ultimately forming a small-diameter, evenly distributed bubble cluster. Switching to single liquid sodium rosinate results in insufficient air entrainment capacity, failing to quickly introduce a sufficient number of bubbles. The appropriate amount of evenly distributed microbubbles formed by the combination of the two can absorb the volume expansion stress generated by water freezing during freeze-thaw cycles, reducing structural damage; when the number of bubbles is insufficient and their diameter is too large, the stress absorption capacity decreases, and the freeze-thaw mass loss rate increases. The small number of larger bubbles in Comparative Example 13 had little impact on the overall porosity, and the impermeability grade and compressive strength did not change much. However, due to the uneven distribution of bubbles, there were still some local permeation channels, and the chloride ion migration coefficient was slightly higher.

[0093] Comparative Example 14 (all composite air-entraining agents used were sodium α-alkenyl sulfonate): Sodium α-alkenyl sulfonate alone disrupted the "air-entraining-foam-stabilizing balance." While it had a strong air-entraining capacity, rapidly introducing a large number of air bubbles, it lacked the foam-stabilizing effect of liquid sodium rosinate. The adsorption film formed by sodium α-alkenyl sulfonate on the bubble surface was thin and fragile. During concrete mixing and vibration, the bubbles easily collided and merged into large bubbles, or escaped due to insufficient film strength, ultimately resulting in a large number of unevenly distributed and large-sized air bubbles inside the concrete. From the perspective of freeze-thaw resistance, the large air bubbles not only failed to effectively absorb freeze-thaw stress but also became "containers" for moisture accumulation. During freeze-thaw cycles, the moisture inside the bubbles would freeze and expand, easily causing cracks in the cement paste around the bubbles. Therefore, the freeze-thaw quality loss rate was higher than that of the example. Large-sized air bubbles significantly increased the interconnected porosity inside the concrete, increasing the number of permeation channels. Large air bubbles were equivalent to "internal defects," weakening the structural integrity of the concrete and reducing its compressive strength. In addition, after the bubbles escape, tiny pits easily form on the surface, increasing the surface area for moisture adsorption and further increasing the probability of intrusion by corrosive media such as chloride ions and sulfates.

[0094] Comparative Example 15 (the ratio of composite air-entraining agent was changed to liquid sodium rosinate: sodium α-alkenyl sulfonate = 1:5): The design logic of the formulation of the example was "to stabilize bubbles and control air-entraining efficiency". The high proportion of liquid sodium rosinate can ensure that the bubbles introduced by sodium α-alkenyl sulfonate are stable and evenly distributed. However, the formulation of Comparative Example 15 broke this balance. The bubble-stabilizing ability of liquid sodium rosinate could not match the high air-entraining ability of sodium α-alkenyl sulfonate, resulting in a bubble structure of "many large bubbles and few small bubbles". The bubble distribution was relatively uneven, which affected the decline of various indicators.

Claims

1. An anti-erosion hydraulic concrete, characterized in that, The concrete comprises the following raw materials in parts by weight: 200-220 parts composite cement, 30-40 parts high-activity nano-modified metakaolin, 80-100 parts blast furnace slag powder, 70-80 parts low-calcium fly ash, 1050-1100 parts coarse aggregate, 650-700 parts natural river sand fine aggregate, 80-100 parts granite manufactured sand fine aggregate, 10-15 parts erosion inhibitor, 10-15 parts functional additives, 5-7 parts early-strength polycarboxylic acid high-performance water-reducing agent, 0.06-0.09 parts composite air-entraining agent, and 135-150 parts water; The composite cement is made of sulfoaluminate cement, silicate cement and polymer waterproof mortar in a mass ratio of 1:(1.4~1.6):(0.2~0.3); The highly active nano-modified metakaolin is obtained by drying metakaolin after modification with an organosilicon-ZnO composite emulsion; the organosilicon-ZnO composite emulsion is formulated with water, polyether-modified organosilicon emulsion, KH-570 silane coupling agent and nano ZnO. The coarse aggregate is composed of basalt crushed stone and granite crushed stone in a mass ratio of 1:(1~1.5); The corrosion inhibitor is composed of an organic carboxylate, a hydrophobic-crystallizing composite agent, and a pH-buffered corrosion inhibitor in a mass ratio of (1.0–1.5):(3.0–4.5):(1.7–2.4); the organic carboxylate is composed of sodium citrate and potassium tartrate in a mass ratio of (2–2.5):(1–1.2); the hydrophobic-crystallizing composite agent is composed of hydrophobic nano-silica and crystalline active component CaSiO3 in a mass ratio of 1:(1–1.5); the pH-buffered corrosion inhibitor is composed of sodium molybdate and cyclohexylamine in a mass ratio of (4–5):

1. The functional additive is composed of itaconic acid acrylic copolymer, JRY-F concrete waterproofing agent and polyethylene glycol-400 dilaurate in a mass ratio of 3:(1-1.5):(0.6-0.8). The composite air-entraining agent is made by mixing liquid sodium rosinate and sodium α-olefin sulfonate in a mass ratio of 5:(1 to 1.5).

2. The anti-erosion hydraulic concrete according to claim 1, characterized in that, The preparation method of the highly active nano-modified metakaolin includes: mixing metakaolin with organosilicon-ZnO composite emulsion evenly, drying, and air-jet pulverizing to a D50 of less than 3 μm to obtain highly active nano-modified metakaolin.

3. The anti-erosion hydraulic concrete according to claim 2, characterized in that, The metakaolin has a particle size that passes through a 650-800 mesh sieve; the amount of the organosilicon-ZnO composite emulsion is 15%-20% of the mass of the metakaolin; the organosilicon-ZnO composite emulsion is prepared by mixing water, polyether-modified organosilicon emulsion, KH-570 silane coupling agent, and nano-ZnO in a mass ratio of 10:(3-5):(0.5-0.8):(1.5-2), and adjusting the pH to 8.3-8.8; the solid content of the polyether-modified organosilicon emulsion is 60wt%-65wt%; and the drying temperature is 60℃-65℃.

4. The anti-erosion hydraulic concrete according to claim 1, characterized in that, The D50 of the blast furnace slag powder is below 10μm.

5. The anti-erosion hydraulic concrete according to claim 1, characterized in that, The low-calcium fly ash has a D50 of less than 50 μm and a CaO content of less than 5 wt%.

6. The anti-erosion hydraulic concrete according to claim 1, characterized in that, The continuous gradation of the coarse aggregate is as follows: 5mm ≤ particle size < 10mm accounts for 30wt% to 35wt%, 10 ≤ particle size < 18mm accounts for 35wt% to 40wt%, and 18 ≤ particle size < 25mm accounts for 25wt% to 30wt%.

7. The anti-erosion hydraulic concrete according to claim 1, characterized in that, The discontinuous gradation of the natural river sand fine aggregate is as follows: 35wt% to 40wt% of the 40-50 mesh range, 45wt% to 50wt% of the 60-80 mesh range, and 15wt% to 20wt% of the 100-120 mesh range.

8. The anti-erosion hydraulic concrete according to claim 1, characterized in that, The discontinuous gradation of the manufactured fine aggregate of the granite is as follows: 60wt% to 70wt% of the 50-mesh to 70-mesh range, and 30wt% to 40wt% of the 100-mesh to 150-mesh range.

9. The anti-erosion hydraulic concrete according to claim 1, characterized in that, The water specifications are: chloride ion content <200mg / L, sulfate ion content <600mg / L.

10. The method for preparing erosion-resistant hydraulic concrete according to claim 1, characterized in that, Includes the following steps: S1: Mix composite cement, blast furnace slag powder and low-calcium fly ash according to the mass fraction to obtain the mixture; S2: Mix coarse aggregate, natural river sand fine aggregate, and granite manufactured sand fine aggregate according to the mass fraction; then add 70wt%~80wt% water, early-strength polycarboxylic acid high-performance water-reducing agent and composite air-entraining agent, and mix; then add the mixture, highly active nano-modified metakaolin, erosion inhibitor and functional additives, and mix; finally add the remaining water, mix, and obtain concrete.

Images