Large-volume air entraining concrete for ship lock and pouring, vibrating and exhausting method

Abstract

The invention discloses ship lock large-volume air-entraining concrete and a pouring vibration exhaust method, and belongs to the technical field of concrete.The ship lock large-volume air-entraining concrete is prepared from 130-160 kg / m < 3 > of cement, 50-70 kg / m < 3 > of fly ash, 50-70 kg / m < 3 > of mineral powder, 600-750 kg / m < 3 > of sand, 1300-1500 kg / m < 3 > of gravel, 3-5 kg / m < 3 > of a water reducing agent, 90-130 kg / m < 3 > of water and 3-4 kg / m < 3 > of an air-entraining anti-cracking agent according to the mixing proportion; a nano-scale super absorbent material is adopted as an air-entraining anti-cracking agent, internal humidity is maintained and a temperature peak value is reduced through water absorption and slow water release, and corresponding nano micropores are reserved in a microstructure through water release and polymer shrinkage, so that the effects of enhancing mechanical properties and resisting cracking after air entraining are achieved.

Description

Technical Field

[0001] This invention belongs to the field of concrete technology, specifically relating to large-volume air-entrained concrete for ship locks and a method for pouring, vibrating, and venting. Background Technology

[0002] As a key structure in hydraulic engineering, ship locks play a vital role in regulating water levels and ensuring navigation. Their foundations and walls are typically constructed using large-volume concrete pours. Due to their large volume and high cement content, the heat of hydration is significant. The heat released during cement hydration can raise the internal temperature of the concrete to 50-70 °C, while the external surface dissipates heat more quickly, creating a large temperature difference and leading to thermal stress. Furthermore, the hydration reaction consumes water, and early water loss triggers self-shrinkage. The combined effect of these two factors easily leads to harmful cracks (width > 0.2 mm), affecting the durability and safety of the ship lock structure.

[0003] To mitigate the temperature difference and shrinkage stress caused by hydration heat, traditional methods include optimizing the mix proportions (reducing cement usage, adding fly ash or slag), pre-embedding cooling pipes (to introduce cooling water for temperature reduction), and layered pouring. However, these methods have limitations: cooling pipe construction is complex and costly, layered pouring may prolong the construction period, and it is difficult to completely solve the problem of internal humidity imbalance. In recent years, superabsorbent polymers (SAPs) have been introduced into mass concrete as internal curing agents. They maintain internal humidity and reduce temperature peaks by absorbing and slowly releasing water. Furthermore, after the release of water, the polymer shrinks, retaining corresponding micropores in the microstructure, which enhances mechanical properties and crack resistance after air entrainment. Existing superabsorbent polymers (SAPs) have certain effects on water retention and crack resistance, but they have the following significant disadvantages in the application of large-volume concrete for ship locks: 1) The pores are unevenly distributed and their size is uncontrollable, with most particles being in the micrometer range. Large-volume concrete for ship locks requires high crack resistance, and the pores need to be uniform and small in size; 2) Excessive particle shrinkage leads to poor structural stability. Large-volume concrete requires SAP particles to maintain a certain structural stability after dehydration to ensure the uniformity of micropores and the mechanical properties of the matrix; 3) The water release rate is difficult to control precisely, resulting in insufficient mechanical properties and susceptibility to crushing under pressure. Summary of the Invention

[0004] To overcome the shortcomings of the prior art, the present invention provides a method for pouring, vibrating and venting large-volume air-entrained concrete for ship locks. The present invention uses nano-level highly absorbent materials as air-entraining and crack-resistant agents. By absorbing water and slowly releasing water, the internal humidity is maintained and the temperature peak is reduced. After the water is released, the polymer shrinks and retains the corresponding nanopores in the microstructure, which enhances the mechanical properties and crack resistance after air entrainment.

[0005] The technical solution to achieve the purpose of this invention is as follows: Large-volume air-entrained concrete for ship locks, with raw materials including 130-160 kg / m³ of cement, based on the mix proportion. 350~70 kg / m³ of fly ash 3 Mineral powder 50~70 kg / m 3 Sand 600~750 kg / m 3 Crushed stone 1300~1500 kg / m³ 3 Water-reducing agent 3~5 kg / m 3 Water 90~130 kg / m 3 3~4 kg / m³ of air-entraining anti-cracking agent 3 ; The preparation steps of the air-entraining and crack-resistant agent are as follows: S1. Preparation of rigid core: prepared by ring-opening metasomatic polymerization of monomer A and monomer B; S2. Grafting of linear outer arm: The monomer C is grafted onto the rigid core through atom transfer radical polymerization to obtain an air-entraining and crack-resistant agent; The structure of monomer A is shown in Equation I below: Formula I; In Formula I, R1 and R2 are independently one or more of H, Na and K, and a is one or more integers from 1 to 5; The monomer B has at least one of the following structures: Formula II , Formula II; In Formula II, R3 and R5 are independently one or more of H, Na and K, R4 and R6 are independently one of Cl and Br, b is one or more of integers from 1 to 5, and c is one or more of integers from 1 to 5. The monomer C has the following structure, Formula III: Formula III; in Formula III, R7 is at least one of H and methyl; R8 is one or more of H and hydrophilic groups.

[0006] Preferably, the water is an ice-water mixture, and the ice content of the ice-water mixture is 50~70 kg / m³. 3 ; Preferably, the preparation step S1 of the air-entraining anti-cracking agent is specifically operated as follows: Under an inert gas atmosphere, monomer A, monomer B, and Grubbs catalyst were dispersed in dichloromethane and added to a reactor. After reacting at 25-50 °C for 30-120 min, monomer B was dispersed in dichloromethane and added to the reaction system. The reaction was continued for another 30-120 min. A terminator was added to end the reaction. After removing the solvent, the resulting solid was washed with alcohol and dried to obtain a rigid core.

[0007] Preferably, the preparation step S2 of the air-entraining anti-cracking agent is specifically operated as follows: In the reactor, the rigid core obtained in step S1 is used as an initiator. Monomer C, catalyst and solvent are added. After freeze-thaw degassing, ligands are added under an inert gas atmosphere. The reaction is carried out at 50~70 ℃ for 6~24 h. Oxygen is introduced to terminate the reaction. After removing the solvent, the solid obtained is washed with cold methanol and dried to obtain the gas-entraining anti-cracking agent. The mass ratio of monomer B, catalyst, and ligand is (800~1200): (0.8~1.2): (1.0~2.0). The catalyst is at least one of bromide ketone and cuprous chloride; The ligand is N,N,N',N',N''-pentamethyldiethylenetriamine; The solvent is anisole.

[0008] Preferably, the mass ratio of monomer A, monomer B and monomer C is (8~12):(1~3):(80~120); the mass ratio of monomer A and Grubbs catalyst is (80~120):(0.8~1.2); the hydrophilic group in monomer C is one or more of polyethylene glycol, polyethylene glycol monomethyl ether and quaternary ammonium salt structures.

[0009] This invention also discloses the above-mentioned method for pouring, vibrating, and venting large-volume air-entrained concrete for ship locks, comprising the following steps: 1) Disperse the air-entraining crack-resistant agent in water. Add cement, fly ash, mineral powder, sand and crushed stone to a cement mixer and mix for 1-2 minutes. Then add the ice-water mixture and mix for 2-5 minutes. Add the water-reducing agent and the air-entraining crack-resistant agent dispersed in water and continue mixing until the ice is fully melted. 2) Concrete is poured in layers using a pump truck, with each layer being 30-50 cm thick and evenly distributed. The interval between layers is 2-4 hours. Before each layer is poured, a thin layer of water mist is sprayed on the surface of the lower layer to increase humidity. 3) Use a high-frequency insertion vibrator with a fast insertion and slow withdrawal method for compaction. The insertion depth should reach 5-10cm to the lower layer of concrete, and the compaction time at each point should be 15-20 seconds with a spacing of 30-40cm. 4) During the compaction process, use a plate vibrator to gently vibrate the surface for 5-10 seconds to promote the uniform distribution of internal microbubbles; 5) Water cooling: The horizontal spacing between cooling water pipes is 1.2~1.5 m; the cooling water temperature is controlled at no higher than 20 ℃; and the water flow rate is no less than 2.0 m³ / h. 3 / h, the cooling water direction should be changed once every 24 hours; 6) Curing: For flat and sloping surfaces, keep the surface warm and moist: After watering, cover with a high-polymer water-saving and moisturizing curing film, and then cover with an insulation board; For vertical surfaces, cover the vertical surfaces with a high-polymer water-saving and moisturizing curing film, hang insulation boards or tarpaulins on the outside, seal the top of the structure with insulation boards, spray the top for curing, and the curing period shall not be less than 28 days.

[0010] Preferably, in step 1), the crack-resistant agent is dispersed in water in a ratio of 1 kg of crack-resistant agent to 8-12 kg of room temperature water.

[0011] Preferably, the vibration frequency in step 3) is 100~150 Hz and the amplitude is 0.5~1.0 mm.

[0012] Preferably, the frequency of the plate vibrator in step 4) is 50~60 Hz.

[0013] Beneficial effects

[0014] This invention offers the following advantages: It utilizes a nanoscale superabsorbent material as an air-entraining and crack-resistant agent. Through water absorption and slow release, it maintains internal humidity and reduces temperature peaks. Furthermore, after water release, the polymer shrinks, retaining corresponding micropores in its microstructure, thus enhancing mechanical properties and crack resistance after air entrainment. The superabsorbent material has a core-shell structure, where the rigid core restricts overall shrinkage and does not completely collapse after dehydration, while the outer shell shrinks to form micropores. Both the core and shell contain water-absorbing groups, with the core exhibiting a cross-linked structure that releases water slowly, creating a gradient release and delaying the heat of hydration. The core-shell structure separates water absorption and support functions; the outer shell has high water absorption, the core has low shrinkage, and the overall particle size is controllable. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the synthesis route of the air-entraining and crack-resistant agent of the present invention. Detailed Implementation

[0016] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0017] Unless otherwise specified, the experimental methods used in the embodiments are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0018] The raw materials and equipment used in the embodiments and comparative examples are described below: Cement: Medium-heat silicate cement, P.MH 42.5, purchased from China Resources Cement; Fly ash: Fineness (residue on 45um square-hole sieve) is 21.8%, Guodian Shenneng Huayingshan Power Generation Co., Ltd.; Iron ore powder: S95 iron ore powder, purchased from Yangchun New Iron & Steel Co., Ltd. of Xiangtan Iron & Steel Co., Ltd. Sand: Grade II medium sand, purchased from Liuzhou city; Crushed stone: 5-20mm, 20-40mm, and 40-80mm graded crushed stone, purchased from Liuzhou City; Water-reducing agent: Polycarboxylate superplasticizer, PCA®-Ⅳ, purchased from Jiangsu Subote; Water: Tap water, meeting the requirements of standard "Mixing Water for Concrete" (JGJ 63-2006); Ice crushing: Flake ice unit, model FIP63E; Chiller: Chiller unit, model LS-510; Acrylic acid: purchased from Anaiji Chemical; Nadic anhydride: purchased from Shanghai Bide; Ethylenediamine monohydrate: purchased from Shanghai Kee Chemical Co., Ltd. Ethanolamine: purchased from Anaiji Chemical; 2-Bromoisobutyryl bromide: purchased from Shanghai Jizhi Biochemical; Catalyst: Brominated ketone, purchased from Aladdin Shanghai; N,N,N`,N`,N``-Pentamethyldiethylenetriamine: purchased from Shanghai Maclean; Grubbs catalyst: Grubbs second-generation catalyst, purchased from Shanghai Bid Pharmaceutical; Nano silica: 100 nm, purchased from Zhejiang Manli Nanotechnology; Terminator: Vinyl ethyl ether, purchased from Shanghai Maclean.

[0019] Monomer A 1 mol of ethylenediamine monohydrate was dispersed in anhydrous tetrahydrofuran, and then 2.2 mol of nadic anhydride was added. After reacting at room temperature for 24 h, the solid was collected by filtration, washed with ethyl acetate, and dried to obtain monomer A.

[0020] Monomer B 1 mol of ethanolamine was dispersed in anhydrous tetrahydrofuran, and then 1.2 mol of Nadic anhydride was added. After reacting at room temperature for 24 h, the solid was collected by filtration, washed with water, and dried. The product was then dispersed in dichloromethane under a nitrogen atmosphere and at 0 °C. 2.0 mol of triethylamine was added, and then 2-bromoisobutyryl bromide was slowly added dropwise. The reaction was continued to be stirred at room temperature for 18 h. The organic phase was washed with hydrochloric acid to remove the solvent, and the resulting solid was recrystallized from ethyl acetate to obtain monomer B.

[0021] Monomer C: Acrylic acid.

[0022] Modified nano silica 2-Bromoisobutyryl bromide was used to modify nano-silica through an acylation reaction, thereby introducing an initiating group.

[0023] Preparation Example 1 S1. Preparation of rigid core: Under a nitrogen atmosphere, 1 mol of monomer A, 0.1 mol of monomer B and 0.01 mol of Grubbs catalyst were dispersed in dichloromethane and added to a reactor. After reacting at 30 °C for 60 min, 0.05 mol of monomer B was dispersed in dichloromethane and added to the reaction system. The reaction was continued for 30 min. A terminator was added to end the reaction. After removing the solvent, the resulting solid was washed with methanol and dried to obtain the rigid core. S2. Grafting of linear outer arms: In a reactor, the rigid core obtained in step S1 was used as an initiator, and 8 mol of monomer C, 0.010 mol of catalyst and benzyl alcohol were added. After freeze-thaw degassing, 0.015 mol of ligand was added under an inert gas atmosphere. After reacting at 60 °C for 18 h, oxygen was introduced to terminate the reaction. After removing the solvent, the obtained solid was washed with cold methanol and dried to obtain gas-entraining anti-cracking agent 1.

[0024] Preparation Example 2 Compared with the preparation method of Preparation Example 1, the difference is that step S1 "reacting at 30 °C for 60 min" is replaced with "reacting at 30 °C for 90 min", to obtain air-entraining anti-cracking agent 2.

[0025] Preparation Example 3 Compared with the preparation method of Preparation Example 1, the difference is that step S1 "reacting at 30 °C for 60 min" is replaced with "reacting at 30 °C for 120 min", to obtain air-entraining anti-cracking agent 3.

[0026] Preparation Example 4 Compared with the preparation method of Preparation Example 1, the difference is that step S2 "8 mol of monomer C" is replaced with "10 mol of monomer C", resulting in air-entraining and crack-resistant agent 4.

[0027] Preparation Example 5 Compared with the preparation method of Preparation Example 1, the difference is that step S2 "8 mol of monomer C" is replaced with "12 mol of monomer C", and air-entraining anti-cracking agent 5 is obtained.

[0028] Preparation Example 6 Compared with the preparation method of Preparation Example 1, the difference is that only step S1 is performed to obtain air-entraining anti-cracking agent 6.

[0029] Preparation Example 7 Compared with the preparation method of Preparation Example 1, the difference is that the "rigid core" in step S2 is replaced with "modified nano silica", resulting in air-entraining and crack-resistant agent 7.

[0030] The following are the test methods for performance parameters involved in this invention: Particle size testing during drying: performed using transmission electron microscopy (TEM); Particle size test after water absorption: The air-entraining crack-resistant agent was dispersed in a 1 M calcium chloride solution to simulate a concrete environment, and the particle size was analyzed using a laser particle size analyzer. Determination of water absorption rate: Accurately weigh 0.1 g of sample into a 500 ml beaker, add 400 ml of deionized water, and let stand at room temperature for 24 h until it reaches saturation. After filtration, let stand for 30 min until no more liquid drips. Weigh the mass of the anti-cracking agent after swelling equilibrium and calculate according to Formula I:

[0031] —Water absorption rate, in g·g -1 ; M1—The total mass of the gel and filter bag when saturated with water, in grams; M2—Mass of the dried filter bag; in grams; M0—Mass of the dried sample, in grams.

[0032] Temperature monitoring: The specimen size is 1000 mm × 1000 mm × 1000 mm. According to JTS-T 202-1-2022 "Overview of Technical Specification for Temperature Crack Control of Large Volume Concrete in Water Transport Engineering", the internal and external temperatures of the concrete are monitored and calculated. Pre-embedded temperature measuring elements are used to directly reflect the internal temperature of the concrete pouring body at the upper, middle and lower height positions of the concrete. Nine measuring points are arranged from the surface to the inside of each layer, and a total of 27 measuring points are arranged for each level of the foundation to monitor the highest temperature of the concrete and the temperature difference between the inner and outer surfaces in real time. Compressive strength: The specimen size is 150 mm × 150 mm × 150 mm, and the test is conducted in accordance with the relevant provisions of standard GB / T 50081-2019; Cracks: Cracks are measured using a standard dot-line gauge, film ruler, comparison card, and feeler gauge; the maximum crack size is recorded. Mercury intrusion porosimetry test: The mercury intrusion test samples were prepared according to the concrete mix proportion of the example agent. The paste specimens were mixed and placed in a cubic grid with a side length of 1 cm. The curing method was the same as that of concrete. When the specified age was reached, the samples were taken out, dried and tested with a mercury intrusion porosimetry instrument.

[0033] Table 1 Performance Test of Air-Entraining Crack-Resistant Agent

[0034] It should be noted that the particle size measured by TEM is mainly the core particle size. Table 1 shows that the core size is related to the reaction time; within a certain range, the longer the reaction time, the larger the core particle size, and the larger the core, the slightly increased the water absorption rate. Data from preparation examples 1, 4, and 5 show that the particle size and water absorption rate after water absorption gradually increase with the increase of the monomer C ratio. Preparation example 6 shows that the expansion rate of the core particles after water absorption is relatively small. Preparation example 7 shows that the air-entraining and crack-resistant agent 7 prepared from rigid nano-silica has a low water absorption rate, because the internal nano-silica does not possess water-absorbing groups.

[0035] The method for vibrating and venting large-volume air-entrained concrete pouring in ship locks includes the following steps: 1) Disperse the air-entraining crack-resistant agent in water. Disperse 1 kg of crack-resistant agent in 10 kg of room temperature water. Add cement, fly ash, mineral powder, sand and gravel to a cement mixer and stir for 2 minutes. Then add the ice-water mixture and stir for 3 minutes. Add the water-reducing agent and the air-entraining crack-resistant agent dispersed in the water. Continue stirring until the ice is fully melted. 2) Concrete is poured in layers using a pump truck, with each layer being 40 cm thick and evenly distributed. There is a 3-hour interval between layers. Before each layer is poured, a thin layer of water mist is sprayed on the surface of the lower layer to increase humidity. 3) A high-frequency insertion vibrator is used for compaction using the fast insertion and slow withdrawal method. The insertion depth reaches 8cm of the lower layer of concrete, the compaction time at each point is 20s, the spacing is 35cm, the compaction frequency is 130 Hz, and the amplitude is 0.8 mm. 4) During the compaction process, use a plate vibrator to gently vibrate the surface for 8 seconds at a frequency of 50 Hz to promote the uniform distribution of internal microbubbles; 5) Water cooling: The horizontal spacing of the cooling water pipes is 1.5 m. The cooling water temperature is controlled at no higher than 20 ℃, and the water flow rate is no less than 2.0 m³ / h. 3 / h, the cooling water direction should be changed once every 24 hours; 6) Curing: For flat and sloping surfaces, keep the surface warm and moist: After watering, cover with a high-polymer water-saving and moisturizing curing film, and then cover with an insulation board; For vertical surfaces, cover the vertical surfaces with a high-polymer water-saving and moisturizing curing film, hang insulation boards or tarpaulins on the outside, seal the top of the structure with insulation boards, spray the top for curing, and the curing period shall not be less than 28 days.

[0036] Table 2. Formula for large-volume air-entrained concrete in ship locks (kg / m³) 3 )

[0037] Table 3 Concrete Performance Tests

[0038] As shown in Table 3, the addition of the air-entraining crack-resistant agent prepared according to this invention can effectively reduce the temperature difference between the inside and outside of concrete, with a maximum temperature difference not exceeding 20 ℃, and increase the porosity and the proportion of <500 nm and 0.5 μm~10 μm pores. Data from Examples 3-5 show that, within a certain range, the larger the core particle size of the air-entraining crack-resistant agent, the higher the compressive strength of the concrete. Data from Examples 3, 6, and 7 show that, within a certain range, the higher the water absorption rate, the lower the maximum temperature difference. Comparative Examples 1 and 2 show that neither adding nor adding too much of the air-entraining crack-resistant agent of this invention will affect the performance of the concrete. Comparative Example 4 shows that when modified nano-silica is used as the core, the maximum temperature difference is higher. This is because the core has a hydrophobic structure, and its water absorption capacity is not as good as the core designed by the air-entraining crack-resistant agent of this invention.

[0039] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. Large-volume air-entrained concrete for ship locks, characterized in that, Based on the mix proportion, the raw materials include 130~160 kg / m³ of cement. 3 50~70 kg / m³ of fly ash 3 Mineral powder 50~70 kg / m 3 Sand 600~750 kg / m 3 Crushed stone 1300~1500 kg / m³ 3 Water-reducing agent 3~5 kg / m 3 Water 90~130 kg / m 3 3~4 kg / m³ of air-entraining anti-cracking agent 3 ; The preparation steps of the air-entraining and crack-resistant agent are as follows: S1. Preparation of rigid core: prepared by ring-opening metasomatic polymerization of monomer A and monomer B; S2. Grafting of linear outer arm: The monomer C is grafted onto the rigid core through atom transfer radical polymerization to obtain an air-entraining and crack-resistant agent; The structure of monomer A is shown in Equation I below: Formula I; In Formula I, R1 and R2 are independently one or more of H, Na and K, and a is one or more integers from 1 to 5; The monomer B has at least one of the following structures: Formula II , Formula II; In Formula II, R3 and R5 are independently one or more of H, Na and K, R4 and R6 are independently one of Cl and Br, b is one or more of integers from 1 to 5, and c is one or more of integers from 1 to 5. The monomer C has the following structure, Formula III: Formula III; in Formula III, R7 is at least one of H and methyl; R8 is one or more of H and hydrophilic groups.

2. The large-volume air-entrained concrete for ship locks as described in claim 1, characterized in that, The water is an ice-water mixture, and the ice content of the ice-water mixture is 50~70 kg / m³. 3 .

3. The large-volume air-entrained concrete for ship locks as described in claim 1, characterized in that, The specific operation of step S1 in preparing the air-entraining and crack-resistant agent is as follows: Under an inert gas atmosphere, monomer A, monomer B, and Grubbs catalyst were dispersed in dichloromethane and added to a reactor. After reacting at 25-50 °C for 30-120 min, monomer B was dispersed in dichloromethane and added to the reaction system. The reaction was continued for another 30-120 min. A terminator was added to end the reaction. After removing the solvent, the resulting solid was washed with alcohol and dried to obtain a rigid core.

4. The large-volume air-entrained concrete for ship locks as described in claim 1, characterized in that, The specific operation of step S2 in preparing the air-entraining and crack-resistant agent is as follows: In the reactor, the rigid core obtained in step S1 is used as an initiator. Monomer C, catalyst and solvent are added. After freeze-thaw degassing, ligands are added under an inert gas atmosphere. The reaction is carried out at 50~70 ℃ for 6~24 h. Oxygen is introduced to terminate the reaction. After removing the solvent, the solid obtained is washed with cold methanol and dried to obtain the gas-entraining anti-cracking agent. The mass ratio of monomer B, catalyst, and ligand is (800~1200): (0.8~1.2): (1.0~2.0). The catalyst is at least one of bromide ketone and cuprous chloride; The ligand is N,N,N',N',N''-pentamethyldiethylenetriamine; The solvent is anisole.

5. The large-volume air-entrained concrete for ship locks as described in claim 1, characterized in that, The mass ratio of monomer A, monomer B and monomer C is (8~12):(1~3):(80~120); the mass ratio of monomer A and Grubbs catalyst is (80~120):(0.8~1.2); the hydrophilic group in monomer C is one or more of polyethylene glycol, polyethylene glycol monomethyl ether and quaternary ammonium salt structures.

6. The method for pouring, vibrating, and venting large-volume air-entrained concrete for ship locks as described in claims 1-5, characterized in that, Includes the following steps: 1) Disperse the air-entraining crack-resistant agent in water. Add cement, fly ash, mineral powder, sand and crushed stone to a cement mixer and mix for 1-2 minutes. Then add the ice-water mixture and mix for 2-5 minutes. Add the water-reducing agent and the air-entraining crack-resistant agent dispersed in water and continue mixing until the ice is fully melted. 2) Concrete is poured in layers using a pump truck, with each layer being 30-50 cm thick and evenly distributed. The interval between layers is 2-4 hours. Before each layer is poured, a thin layer of water mist is sprayed on the surface of the lower layer to increase humidity. 3) Use a high-frequency immersion vibrator with a fast insertion and slow withdrawal method for compaction. The insertion depth should reach 5-10 cm to the lower layer of concrete, and the compaction time at each point should be 15-20 s with a spacing of 30-40 cm. 4) During the compaction process, use a plate vibrator to gently vibrate the surface for 5-10 seconds to promote the uniform distribution of internal microbubbles; 5) Water cooling: The horizontal spacing between cooling water pipes is 1.2~1.5 m; the cooling water temperature is controlled at no higher than 20 ℃; and the water flow rate is no less than 2.0 m³ / h. 3 / h, the cooling water direction should be changed once every 24 hours; 6) Curing: For flat and sloping surfaces, keep the surface warm and moist: After watering, cover with a high-polymer water-saving and moisturizing curing film, and then cover with an insulation board; For vertical surfaces, cover the vertical surfaces with a high-polymer water-saving and moisturizing curing film, hang insulation boards or tarpaulins on the outside, seal the top of the structure with insulation boards, spray the top for curing, and the curing period shall not be less than 28 days.

7. The method for pouring, vibrating, and venting large-volume air-entrained concrete for ship locks as described in claim 6, characterized in that, Step 1) The anti-cracking agent is dispersed in water by dispersing 1 kg of anti-cracking agent in 8-12 kg of room temperature water.

8. The method for pouring, vibrating, and venting large-volume air-entrained concrete for ship locks as described in claim 6, characterized in that, Step 3) The vibration frequency is 100~150 Hz and the amplitude is 0.5~1.0 mm.

9. The method for pouring, vibrating, and venting large-volume air-entrained concrete for ship locks as described in claim 6, characterized in that, Step 4) The frequency of the plate vibrator is 50~60 Hz.

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