High-performance anticorrosive concrete for marine engineering and method for preparing the same

Abstract

The application relates to the technical field of concrete, and specifically discloses high-performance anticorrosive concrete for ocean engineering and a preparation method thereof. The concrete disclosed by the application comprises the following components: 7000-8000 parts of sulphoaluminate cement, 1400-2000 parts of gravel, 1200-1800 parts of fly ash, 1000-1400 parts of silica ash, 200-300 parts of corrosion-resistant functional additives, 100-200 parts of reinforcing materials, 10-20 parts of water reducing agents, 4-10 parts of retarders and 3000-4000 parts of water; the corrosion-resistant functional additives are composed of calcium nitrite, vinyl ester resin and organic phosphate; and the reinforcing materials are obtained by modifying basalt fibers with zinc salt, aluminum salt and silane. The above technical scheme improves the chloride ion penetration resistance and sulphate corrosion resistance of the concrete, and enhances the structural stability and service life of the concrete in the marine environment.

Description

Technical Field

[0001] This application relates to the technical field of concrete, specifically to a high-performance anti-corrosion concrete for marine engineering and its preparation method. Background Technology

[0002] Traditional concrete used in marine engineering is prone to performance degradation, such as decreased strength and structural damage, under long-term seawater erosion, salt corrosion, and extreme environmental influences. Existing anti-corrosion concrete often relies on high-volume mineral admixtures or organic coatings, which result in high costs, complex construction, or insufficient long-term performance.

[0003] Therefore, there is an urgent need for a high-performance concrete that combines high impermeability and chemical corrosion resistance. Summary of the Invention

[0004] To address the aforementioned technical problems, this application provides a high-performance anti-corrosion concrete for marine engineering and its preparation method.

[0005] In one aspect, this application provides a high-performance anti-corrosion concrete for marine engineering, specifically comprising the following components in parts by weight: 7000-8000 parts of sulfoaluminate cement, 1400-2000 parts of crushed stone, 1200-1800 parts of fly ash, 1000-1400 parts of silica fume, 200-300 parts of corrosion-resistant functional additives, 100-200 parts of reinforcing materials, 10-20 parts of water-reducing agent, 4-10 parts of retarder, and 3000-4000 parts of water.

[0006] The corrosion-resistant functional additive is composed of calcium nitrite, vinyl ester resin, and organophosphate in a weight ratio of 10-20:5-9:5-9.

[0007] The method for preparing the reinforcing material is as follows: basalt fibers are modified with a mixed solution containing soluble zinc salt with a molar concentration of 1-2 mol / L, soluble aluminum salt with a molar concentration of 0.2-0.8 mol / L, and silane with a weight concentration of 20-40 g / L to obtain the reinforcing material.

[0008] This application improves the resistance of concrete to chloride ion penetration and sulfate corrosion by introducing highly efficient corrosion-resistant functional additives and reinforcing materials, thereby enhancing its structural stability and service life in marine environments.

[0009] The corrosion-resistant functional additive system in this application embeds calcium nitrite and vinyl ester resin into the concrete matrix to form a barrier network that slows down the chloride ion penetration rate. Through the grain boundary modification effect of organophosphates, it simultaneously improves the microstructure density and crack self-healing ability. The reinforcing material is obtained by modifying basalt fibers with zinc salts, aluminum salts, and silanes. In this modification reaction, zinc salts and aluminum salts can form a dense passivation film on the fiber surface, inhibiting the diffusion of chloride and sulfate ions. They can also reduce the erosion of concrete by free chloride ions through ion exchange reactions. Simultaneously, silanes form a hydrophobic layer on the fiber surface, reducing pore water absorption and blocking ion transport channels. Furthermore, it can enhance the interfacial adhesion between the fiber and the cement matrix, reduce the generation of microcracks, and further enhance the structural stability and service life of concrete in marine environments.

[0010] Preferably, the high-performance anti-corrosion concrete for marine engineering specifically comprises the following components in parts by weight: 7200-7800 parts of sulfoaluminate cement, 1600-1800 parts of crushed stone, 1400-1600 parts of fly ash, 1100-1300 parts of silica fume, 220-260 parts of corrosion-resistant functional additives, 140-180 parts of reinforcing materials, 12-18 parts of water-reducing agent, 6-8 parts of retarder, and 3200-3800 parts of water.

[0011] Preferably, the crushed stone is granite crushed stone with a particle size of 2-10 mm and an apparent density of 2400-2800 kg / m³. 3 The fly ash is Class F, Grade I; the silica fume is silica powder with a specific surface area of ​​28±3 m². 2 / g.

[0012] Preferably, the corrosion-resistant functional additive is composed of calcium nitrite, vinyl ester resin, and organophosphate in a weight ratio of 13-17:6-8:6-8.

[0013] In one specific embodiment, the weight ratio of calcium nitrite, vinyl ester resin, and organophosphate in the corrosion-resistant functional additive is 10:5:5, 20:5:5, 10:6:5, 13:6:5, 15:6:5, 17:6:5, 20:6:5, 10:7:5, 13:7:5, 15:7:5, 17:7:5, 20:7:5, 10:8:5, 13:8:5, 15:8 5, 17:8:5, 20:8:5, 10:9:5, 13:9:5, 15:9:5, 17:9:5, 20:9:5, 10:6:6, 13:6:6, 15:6:6, 17:6:6, 20:6:6, 10:7:7, 13:7:7, 15:7:7, 17:7:7, 10:8:8, 13:8:8, 15:8:8, 17:8:8, 20:8:8.

[0014] Experimental analysis shows that the corrosion-resistant functional additive composed of calcium nitrite, vinyl ester resin, and organophosphate in the above weight ratio can further improve the performance of concrete.

[0015] Preferably, in the corrosion-resistant functional additive, the organic phosphoric acid is selected from any one or more of aminotrimethylene phosphate, ethyltriaminepentamethylene phosphate, ethylenediaminetetramethylene phosphate, hydroxyethylidene diphosphate, and diethylenetriaminepentamethylene phosphate.

[0016] Preferably, the preparation method of the reinforcing material is as follows: prepare a mixed salt solution with molar concentrations of 1.2-1.8 mol / L of soluble zinc salt and 0.4-0.6 mol / L of soluble aluminum salt; under stirring and a water bath temperature of 70-90℃, add basalt fiber to the mixed salt solution to a weight concentration of 90-130 g / L, and add silane to a weight concentration of 25-35 g / L; place the solution in a water bath at 70-90℃ and stir for aging for 4-6 hours; then filter and retain the filter cake; then dry at 80-120℃ and grind to obtain the reinforcing material.

[0017] Preferably, the basalt fiber has the following specifications: a diameter of 20-30 μm and a length of 10-20 mm.

[0018] Preferably, the silane is selected from one or more of propylmethyldiethoxysilane, 3-(2,3-epoxypropoxypropyl)trimethoxysilane, vinyltriethoxysilane, tetramethyltetraethylenecyclotetrasiloxane, and 3-aminopropyltrimethoxysilane.

[0019] Preferably, the water-reducing agent is HS-209 type polycarboxylate water-reducing agent; the retarder is sodium gluconate.

[0020] Secondly, this application provides a method for preparing the aforementioned high-performance anti-corrosion concrete for marine engineering, specifically including the following steps in sequence:

[0021] Mix sulfoaluminate cement, crushed stone, fly ash, and silica fume, add water, and stir evenly; then add corrosion-resistant functional additives, reinforcing materials, water-reducing agents, and retarders, and stir evenly.

[0022] After curing, the high-performance anti-corrosion concrete used in marine engineering is obtained.

[0023] In summary, the technical solution of this application has the following effects:

[0024] This application improves the resistance of concrete to chloride ion penetration and sulfate corrosion by introducing highly efficient corrosion-resistant functional additives and reinforcing materials, thereby enhancing its structural stability and service life in marine environments.

[0025] Compared with existing technologies, the technical solution of this application optimizes the material ratio and additive selection, enabling the concrete to have good comprehensive performance and be suitable for marine environments. Detailed Implementation

[0026] The present application will be further described in detail below with reference to embodiments, comparative examples and performance test results. These embodiments should not be construed as limiting the scope of protection claimed in this application. Example

[0027] Examples 1-5

[0028] Examples 1-5 provide a high-performance anti-corrosion concrete for marine engineering and its preparation method.

[0029] The difference in the above embodiments is that the dosage of each component in the high-performance anti-corrosion concrete is different, as shown in Table 1.

[0030] The preparation method of the high-performance anti-corrosion concrete for marine engineering in the above embodiments is as follows:

[0031] The preparation method of the reinforcing material is as follows: a mixed salt solution with a molar concentration of 1.5 mol / L zinc sulfate and 0.5 mol / L aluminum sulfate is prepared; under stirring and a water bath temperature of 80℃, basalt fibers (basalt fiber specifications: diameter 20-30 μm, length 10-20 mm) are added to the mixed salt solution to a weight concentration of 110 g / L, and 3-aminopropyltrimethoxysilane is added to a weight concentration of 30 g / L. The mixture is then stirred and aged at a water bath temperature of 80℃ for 5 h, filtered, and the filter cake is retained; then dried at 100℃ and ground to a particle size ≤20 mm to obtain the reinforcing material.

[0032] According to Table 1, weigh the corresponding weights of each component raw material, including sulfoaluminate cement and granite crushed stone with a particle size of 2-10mm (apparent density of 2660kg / m³). 3 Class I fly ash (F type), with a specific surface area of ​​28±3 m². 2 Mix / g of silica fume, add water, and stir evenly; then add corrosion-resistant functional additives (the corrosion-resistant functional additives are composed of calcium nitrite, 901 vinyl ester resin (purchased from Shanghai Kaiyin Chemical Co., Ltd.), and hydroxyethylidene diphosphate in a weight ratio of 15:7:7), reinforcing materials, HS-209 polycarboxylate superplasticizer, and sodium gluconate retarder, and stir evenly; after 28 days of curing, high-performance anti-corrosion concrete for marine engineering is obtained.

[0033] Table 1. Dosage of each component in high-performance anti-corrosion concrete in Examples 1-5

[0034]

[0035] Examples 6-9

[0036] Examples 6-9 provide a high-performance anti-corrosion concrete for marine engineering and its preparation method.

[0037] The difference between the above embodiments and Embodiment 1 is that the types of corrosion-resistant functional additives are different, as shown below.

[0038] In Example 6: The corrosion-resistant functional additive is composed of calcium nitrite, vinyl ester resin and organophosphate in a weight ratio of 10:9:5.

[0039] In Example 7: The corrosion-resistant functional additive is composed of calcium nitrite, vinyl ester resin and organophosphate in a weight ratio of 20:9:5.

[0040] In Example 8: The corrosion-resistant functional additive is composed of calcium nitrite, vinyl ester resin and organophosphate in a weight ratio of 13:8:6.

[0041] In Example 9: The corrosion-resistant functional additive is composed of calcium nitrite, vinyl ester resin and organophosphate in a weight ratio of 17:6:8.

[0042] All other process parameters in the above embodiments are the same as those in Embodiment 1.

[0043] Examples 10-13

[0044] Examples 10-13 respectively provide a high-performance anti-corrosion concrete for marine engineering and its preparation method.

[0045] The difference between the above embodiments and Embodiment 1 is that the preparation methods of the reinforcing materials are different, as detailed below.

[0046] In Example 10, the preparation method of the reinforcing material is as follows: a mixed salt solution with a molar concentration of 1 mol / L zinc sulfate and 0.8 mol / L aluminum sulfate is prepared; under stirring and a water bath temperature of 80°C, basalt fiber is added to the mixed salt solution to a weight concentration of 110 g / L, and 3-aminopropyltrimethoxysilane is added to a weight concentration of 30 g / L. The solution is then stirred and aged at a water bath temperature of 80°C for 5 hours, filtered, and the filter cake is retained; then dried at 100°C and ground to obtain the reinforcing material.

[0047] In Example 11, the preparation method of the reinforcing material is as follows: a mixed salt solution with a molar concentration of 2 mol / L zinc sulfate and 0.2 mol / L aluminum sulfate is prepared; under stirring and a water bath temperature of 80°C, basalt fiber is added to the mixed salt solution to a weight concentration of 110 g / L, and 3-aminopropyltrimethoxysilane is added to a weight concentration of 30 g / L. The solution is then stirred and aged at a water bath temperature of 80°C for 5 hours, filtered, and the filter cake is retained; then dried at 100°C and ground to obtain the reinforcing material.

[0048] In Example 12, the preparation method of the reinforcing material is as follows: a mixed salt solution with a molar concentration of 1.5 mol / L zinc sulfate and 0.5 mol / L aluminum sulfate is prepared; under stirring and a water bath temperature of 80°C, basalt fiber is added to the mixed salt solution to a weight concentration of 110 g / L, and 3-aminopropyltrimethoxysilane is added to a weight concentration of 20 g / L. The solution is then stirred and aged at a water bath temperature of 80°C for 5 hours, filtered, and the filter cake is retained; then dried at 100°C and ground to a particle size ≤20 mm to obtain the reinforcing material.

[0049] In Example 13, the preparation method of the reinforcing material is as follows: a mixed salt solution with a molar concentration of 1.5 mol / L zinc sulfate and 0.5 mol / L aluminum sulfate is prepared; under stirring and a water bath temperature of 80°C, basalt fiber is added to the mixed salt solution to a weight concentration of 110 g / L, and 3-aminopropyltrimethoxysilane is added to a weight concentration of 40 g / L. The solution is then stirred and aged at a water bath temperature of 80°C for 5 hours, filtered, and the filter cake is retained; then dried at 100°C and ground to a particle size ≤20 mm to obtain the reinforcing material.

[0050] All other process parameters in the above embodiments are the same as those in Embodiment 1.

[0051] Comparative Example

[0052] Comparative Examples 1-2

[0053] Comparative Examples 1 and 2 respectively provide a high-performance anti-corrosion concrete for marine engineering and its preparation method.

[0054] The difference between the above embodiments and Embodiment 1 is that the dosage of each component in the high-performance anti-corrosion concrete is different, as shown in Table 1.

[0055] All other process parameters in the above comparative examples are the same as those in Example 1.

[0056] Comparative Examples 3-5

[0057] Comparative Examples 3-5 each provide a high-performance anti-corrosion concrete for marine engineering and its preparation method.

[0058] The differences between the above comparative examples and Example 1 are as follows.

[0059] In Comparative Example 3, the corrosion-resistant functional additive was composed of calcium nitrite, BR-106 acrylic resin (purchased from Shanghai Kaiyin Chemical Co., Ltd.) and hydroxyethylidene diphosphonic acid in a weight ratio of 15:7:7.

[0060] In Comparative Example 4, an equal amount of unmodified basalt fiber was used as the reinforcing material.

[0061] In Comparative Example 5: The preparation method of the reinforcing material is as follows: a mixed salt solution with a molar concentration of 0.5 mol / L zinc sulfate and 1.5 mol / L aluminum sulfate is prepared; under stirring and a water bath temperature of 80℃, basalt fibers (basalt fiber specifications: diameter 20-30 μm, length 10-20 mm) are added to the mixed salt solution to a weight concentration of 110 g / L, and 3-aminopropyltrimethoxysilane is added to a weight concentration of 50 g / L. The mixture is then stirred and aged at a water bath temperature of 80℃ for 5 h, filtered, and the filter cake is retained; then it is dried at 100℃ and ground to obtain the reinforcing material.

[0062] All other process parameters in the above comparative examples are the same as those in Example 1.

[0063] Performance testing

[0064] (1) Chloride ion penetration resistance: The chloride ion penetration resistance of concrete was tested according to ASTM C1202-2012.

[0065] (2) Resistance to sulfate corrosion: According to GB / T 50082-2009, the specimen was immersed in a 5wt% Na2SO4 aqueous solution, and the compressive strength loss rate and chloride ion permeability loss rate were determined.

[0066] Test results are shown in Table 2.

[0067] Table 2 Performance test results of concrete in the examples and comparative examples

[0068]

[0069] As can be seen from the test results in Table 2 above, the concrete prepared using the technical solution provided in this application has excellent resistance to chloride ion penetration and sulfate corrosion, and is suitable as a building material for marine engineering.

[0070] By comparing the test results of Examples 1-5 with those of Comparative Examples 1-2, it can be seen that Comparative Example 1 did not add any corrosion-resistant functional additives and reinforcing materials, and the amounts of corrosion-resistant functional additives and reinforcing materials in Comparative Example 2 were mismatched, resulting in concrete with poor resistance to chloride ion penetration and sulfate corrosion. In contrast, this application selects to add specific amounts of corrosion-resistant functional additives and reinforcing materials to the concrete, resulting in concrete with excellent resistance to chloride ion penetration and sulfate corrosion.

[0071] By comparing the test results of Examples 1, 6-9 and Comparative Example 3, it can be seen that the corrosion-resistant functional additive in Comparative Example 3 is composed of calcium nitrite, BR-106 acrylic resin and hydroxyethylidene diphosphate in a weight ratio of 15:7:7. The concrete prepared by this mixture has poor resistance to chloride ion penetration and sulfate corrosion. In contrast, the corrosion-resistant functional additive selected in this application is composed of calcium nitrite, vinyl ester resin and organophosphate in a weight ratio of 10-20:5-9:5-9, which effectively improves the resistance to chloride ion penetration and sulfate corrosion of the concrete.

[0072] By comparing the test results of Examples 1, 10-13 and Comparative Example 3, it can be seen that in Comparative Example 4, an equal amount of unmodified basalt fiber was used as the reinforcing material. In Comparative Example 5, the concentrations of zinc salt, aluminum salt, and silane were mismatched in the preparation method of the reinforcing material, resulting in concrete with poor resistance to chloride ion penetration and sulfate corrosion. In contrast, this application modifies basalt fiber with a mixed solution containing soluble zinc salt (1-2 mol / L), soluble aluminum salt (0.2-0.8 mol / L), and silane (20-40 g / L), effectively improving the concrete's resistance to chloride ion penetration and sulfate corrosion.

[0073] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A high-performance anti-corrosion concrete for marine engineering, characterized in that, Specifically, it includes the following components by weight: 7000-8000 parts of sulfoaluminate cement, 1400-2000 parts of crushed stone, 1200-1800 parts of fly ash, 1000-1400 parts of silica fume, 200-300 parts of corrosion-resistant functional additives, 100-200 parts of reinforcing materials, 10-20 parts of water-reducing agent, 4-10 parts of retarder, and 3000-4000 parts of water. The corrosion-resistant functional additive is composed of calcium nitrite, vinyl ester resin, and organophosphate in a weight ratio of 10-20:5-9:5-9. The reinforcing material is prepared by modifying basalt fibers with a mixed solution containing soluble zinc salt with a molar concentration of 1-2 mol / L, soluble aluminum salt with a molar concentration of 0.2-0.8 mol / L, and silane with a weight concentration of 20-40 g / L.

2. The high-performance anti-corrosion concrete for marine engineering according to claim 1, characterized in that, Specifically, it includes the following components by weight: 7200-7800 parts of sulfoaluminate cement, 1600-1800 parts of crushed stone, 1400-1600 parts of fly ash, 1100-1300 parts of silica fume, 220-260 parts of corrosion-resistant functional additives, 140-180 parts of reinforcing materials, 12-18 parts of water-reducing agent, 6-8 parts of retarder, and 3200-3800 parts of water.

3. The high-performance anti-corrosion concrete for marine engineering according to claim 1, characterized in that, The crushed stone is granite crushed stone with a particle size of 2-10mm and an apparent density of 2400-2800 kg / m³. 3 The fly ash is Class F, Grade I; the silica fume is silica powder with a specific surface area of ​​28±3 m². 2 / g.

4. The high-performance anti-corrosion concrete for marine engineering according to claim 1, characterized in that, The corrosion-resistant functional additive is composed of calcium nitrite, vinyl ester resin, and organophosphate in a weight ratio of 13-17:6-8:6-8.

5. The high-performance anti-corrosion concrete for marine engineering according to claim 1, characterized in that, In the corrosion-resistant functional additive, the organic phosphoric acid is selected from any one or more of aminotrimethylene phosphate, ethyltriaminepentamethylene phosphate, ethylenediaminetetramethylene phosphate, hydroxyethylidene diphosphate, and diethylenetriaminepentamethylene phosphate.

6. The high-performance anti-corrosion concrete for marine engineering according to claim 1, characterized in that, The preparation method of the reinforcing material is as follows: prepare a mixed salt solution with a molar concentration of 1.2-1.8 mol / L of soluble zinc salt and 0.4-0.6 mol / L of soluble aluminum salt; under stirring and a water bath temperature of 70-90℃, add basalt fiber to the mixed salt solution to a weight concentration of 90-130 g / L, and add silane to a weight concentration of 25-35 g / L; place the solution in a water bath at 70-90℃ and stir for aging for 4-6 hours; then filter and keep the filter cake; then dry at 80-120℃ and grind to obtain the reinforcing material.

7. The high-performance anti-corrosion concrete for marine engineering according to claim 1, characterized in that, The specifications of the basalt fiber are: diameter 20-30μm and length 10-20mm.

8. The high-performance anti-corrosion concrete for marine engineering according to claim 1, characterized in that, The silane is selected from one or more of propylmethyldiethoxysilane, 3-(2,3-epoxypropoxypropyl)trimethoxysilane, vinyltriethoxysilane, tetramethyltetraethylenecyclotetrasiloxane, and 3-aminopropyltrimethoxysilane.

9. The method for preparing high-performance anti-corrosion concrete for marine engineering as described in any one of claims 1-8, characterized in that, Specifically, the following steps are performed sequentially: Mix sulfoaluminate cement, crushed stone, fly ash, and silica fume, add water, and stir evenly; then add corrosion-resistant functional additives, reinforcing materials, water-reducing agents, and retarders, and stir evenly. After curing, the high-performance anti-corrosion concrete used in marine engineering is obtained.

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