Graphene modified concrete material and preparation method thereof

Abstract

This invention relates to a graphene-modified concrete material and its preparation method. The material comprises, by weight, the following components: 100 parts cement, 132-224 parts coarse aggregate, 258-386 parts fine aggregate, 23-46 parts fly ash, 6-12 parts modified graphene oxide, 1.8-3.6 parts water-reducing agent, 5-10 parts polypropylene fiber, and 65-85 parts water. This invention prepares a concrete material with added modified graphene oxide. Compared to the traditional method of directly adding graphene or graphene oxide to cement-based composite materials, the modified graphene oxide added in this invention is a product obtained through surface modification treatment. The concrete material prepared using the method of this invention has higher strength and toughness, and is less prone to cracking.

Description

Technical Field

[0001] This invention relates to the field of concrete, specifically to a graphene-modified concrete material and its preparation method. Background Technology

[0002] Concrete, with its advantages of abundant raw materials, low price, simple production process, good durability, high flexural strength, and wide range of strength grades, has a wide range of applications in the construction industry, shipbuilding industry, machinery industry, marine development, geothermal engineering and other fields. With the increasingly rapid modernization of the construction industry, higher performance requirements are being placed on concrete materials, such as higher flexural strength and stronger waterproof performance.

[0003] Currently, methods to improve concrete durability mainly involve using lower water-cement ratios and large amounts of fly ash, slag, and silica fume to improve the properties of hardened concrete and thus enhance its resistance to chloride corrosion. However, research on the structural changes that occur during the cement hydration process has been neglected. Nanomaterials, as an emerging and rapidly developing field of materials science, are widely used in various fields due to the significant impact of small size effects on the physicochemical properties and microstructure of materials, becoming a hot topic in materials science research today. Graphene oxide (GO), an oxidation product of graphite, possesses extremely high strength and flexibility, and an extremely large specific surface area. The structure of GO contains hydroxyl, carboxyl, and epoxy groups, which readily form nano-dispersed sheets. Adding small amounts of graphene or GO to cement-based composite materials can regulate the shape of cement hydration crystal products, resulting in significant reinforcement and toughening effects. This can significantly improve the mechanical properties of cement composite materials, improve pore structure, and enhance resistance to chloride ion penetration.

[0004] However, in actual use, graphene-modified concrete is prone to cracking when exposed to the external environment. This is mainly due to the poor flexibility of the concrete, the poor dispersion of graphene, and the unevenness of the concrete raw materials. Summary of the Invention

[0005] In view of the problems existing in the prior art, the purpose of this invention is to provide a graphene-modified concrete material and its preparation method.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] In a first aspect, the present invention provides a graphene-modified concrete material, comprising the following components by weight:

[0008] 100 parts cement, 132-224 parts coarse aggregate, 258-386 parts fine aggregate, 23-46 parts fly ash, 6-12 parts modified graphene oxide, 1.8-3.6 parts water-reducing agent, 5-10 parts polypropylene fiber and 65-85 parts water.

[0009] The method for preparing the modified graphene oxide includes:

[0010] S1, sulfonation treatment:

[0011] Weigh out p-aminobenzenesulfonic acid and sodium hydroxide solution, mix them, heat to 50-60℃, stir until dissolved and homogeneous, cool to room temperature, add sodium nitrite, stir thoroughly again to obtain mixture A; weigh out hydrochloric acid solution, place it in an ice-water bath, stir for half an hour, add mixture A dropwise, continue stirring for half an hour after the addition is complete, then filter and collect the precipitate to obtain solid B;

[0012] Solid B and deionized water were mixed and stirred thoroughly in an ice-water bath for half an hour. Then graphene oxide was added and stirred for another half hour. The precipitate was collected by filtration, washed with water at least three times, and dried to obtain sulfonated graphene.

[0013] S2, Polymerization Modification Reaction

[0014] Sulfonated graphene was mixed in deionized water and dispersed thoroughly to obtain a sulfonated graphene solution.

[0015] Add sodium hydroxide solution dropwise to formaldehyde solution to maintain the pH of the mixture at 9-10. Then add melamine, heat to 60-70℃, stir for 20-50 minutes, slowly add sulfonic acid graphene solution, continue stirring for 2-4 hours, cool to 35-45℃, and then carry out acid polymerization and basic polymerization reactions in sequence. After the reaction is completed, wash the reaction product with water at least three times and dry it in a vacuum chamber to obtain modified graphene oxide.

[0016] Preferably, the cement is P.O42.5 ordinary Portland cement.

[0017] Preferably, the coarse aggregate is crushed stone or pebbles with a particle size between 4.75-10 mm.

[0018] Preferably, the fine aggregate is river sand or sea sand with a particle size between 0.15 and 4.75 mm.

[0019] Preferably, the fly ash is Class I fly ash.

[0020] Preferably, the water-reducing agent is a polycarboxylate superplasticizer, including models SPC-100 or SPC-101.

[0021] Preferably, the polypropylene fiber has a diameter of 20-30 μm and a length of 15-30 mm.

[0022] Preferably, in S1, the mass fraction of sodium hydroxide solution is 5%, and the mass ratio of p-aminobenzenesulfonic acid, sodium nitrite, and sodium hydroxide solution is 1:0.3-0.5:4-8.

[0023] Preferably, in S1, the mass fraction of the hydrochloric acid solution is 5%, and the mass ratio of the hydrochloric acid solution to the mixture A is 1.2-1.6:1.

[0024] Preferably, in S1, the graphene oxide has an oxygen content of 30%, a purity of >99%, a particle size of 1.5-3μm, a thickness of 1.5-2.2nm, and 2-5 layers.

[0025] Preferably, in S1, the mass ratio of solid B, graphene oxide, and deionized water is 0.3-0.6:1:40-60.

[0026] Preferably, in the S2 sulfonated graphene solution, the mass ratio of sulfonated graphene to deionized water is 1:10-20.

[0027] Preferably, in step S2, the formaldehyde solution has a mass fraction of 37%, and the mass ratio of formaldehyde solution, melamine, and sulfonic acid graphene solution is 2-4:1-2:6-10.

[0028] Preferably, in step S2, the acidic polymerization reaction involves adding sulfuric acid solution dropwise to the reaction solution until the pH of the reaction solution is 5-6, and stirring for half an hour; the alkaline polymerization reaction involves adding sodium hydroxide solution dropwise to the reaction solution after the acidic polymerization reaction until the pH of the reaction solution is 10-11, and stirring for half an hour.

[0029] Preferably, in step S2, the drying temperature inside the vacuum chamber is 60-80°C, and the drying time is 5-10 hours.

[0030] Secondly, the present invention provides a method for preparing graphene-modified concrete material, comprising the following steps:

[0031] Step 1: Weigh out each component according to the weight proportions, mix them into a cement mixer, and mix at a speed of 100-200 r / min for 10-20 min;

[0032] Step 2: Pour the well-mixed slurry from the mixer into the mold, vibrate to degas it, cover the mold with plastic film, keep it at room temperature for at least 24 hours, then demold it and cure it for 14-28 days at a temperature of 22±2℃ and a humidity of 90%±2% to obtain graphene-modified concrete material.

[0033] The beneficial effects of this invention are as follows:

[0034] 1. This invention prepares a concrete material with modified graphene oxide. Compared with the traditional method of directly adding graphene or graphene oxide to cement-based composite materials, the modified graphene oxide added in this invention is a product obtained through surface modification treatment. The concrete material prepared using the method of this invention has higher strength and toughness, and also has the advantages of being waterproof and not prone to cracking.

[0035] 2. The method of graphene modification in this invention involves first preparing p-aminobenzenesulfonic acid diazonium hydrochloride, and then grafting sulfonic acid groups onto the surface of graphene oxide through a diazotization reaction. This sulfonic acid group is then incorporated into the synthesis process of melamine-formaldehyde resin to prepare modified graphene oxide. The modified graphene oxide prepared in this invention uses sulfonated graphene oxide as a reactant, allowing the sulfonic acid groups to participate in the reaction process of melamine-formaldehyde resin. Compared with conventional graphene oxide, the obtained modified graphene oxide exhibits better uniformity and improved performance, resulting in a better improvement effect on the performance of concrete materials. Detailed Implementation

[0036] The technical solution of the present invention is illustrated below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or defining the scope of the present invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the present invention.

[0037] To better understand the above technical solutions, exemplary embodiments of the present invention are described in more detail below. While exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the present invention and to fully convey the scope of the invention to those skilled in the art.

[0038] The present invention will be further described below with reference to the following embodiments.

[0039] Example 1

[0040] A graphene-modified concrete material, comprising the following components by weight:

[0041] 100 parts cement, 185 parts coarse aggregate, 324 parts fine aggregate, 35 parts fly ash, 9 parts modified graphene oxide, 2.7 parts water-reducing agent, 8 parts polypropylene fiber and 75 parts water.

[0042] Wherein, the cement is P.O42.5 ordinary Portland cement; the coarse aggregate is crushed stone with a particle size between 4.75-10mm; the fine aggregate is river sand with a particle size between 0.15-4.75mm; and the fly ash is Grade I fly ash.

[0043] The water-reducing agent is a polycarboxylate superplasticizer, model SPC-101; the polypropylene fiber has a diameter of 20-30 μm and a length of 15-30 mm.

[0044] The method for preparing the modified graphene oxide includes:

[0045] S1, sulfonation treatment:

[0046] Weigh out p-aminobenzenesulfonic acid and a 5% sodium hydroxide solution, mix them, heat to 55°C, stir until dissolved and homogeneous, then cool to room temperature, add sodium nitrite (mass ratio of p-aminobenzenesulfonic acid, sodium nitrite, and sodium hydroxide solution is 1:0.4:6), stir thoroughly again to obtain mixture A; weigh out a 5% hydrochloric acid solution, place it in an ice-water bath, stir for half an hour, then add mixture A dropwise (mass ratio of hydrochloric acid solution to mixture A is 1.4:1), continue stirring for half an hour after the addition is complete, then filter and collect the precipitate to obtain solid B;

[0047] Solid B and deionized water were mixed and stirred thoroughly in an ice-water bath for half an hour. Then, graphene oxide (oxygen content 30%, purity >99%, particle size 1.5-3μm, thickness 1.5-2.2nm, number of layers 2-5) was added and stirred for another half hour. The mass ratio of solid B, graphene oxide and deionized water was 0.4:1:50. The precipitate was collected by filtration, washed with water at least three times, and dried to obtain sulfonated graphene.

[0048] S2, Polymerization Modification Reaction

[0049] Sulfonated graphene was mixed in deionized water at a mass ratio of 1:15. After thorough dispersion, a sulfonated graphene solution was obtained.

[0050] Sodium hydroxide solution was added dropwise to a 37% formaldehyde solution to maintain the pH of the mixture at 9-10. Melamine was then added, and the mixture was heated to 65°C and stirred for 30 minutes. Then, sulfonic acid graphene solution was slowly added. The mass ratio of formaldehyde solution, melamine, and sulfonic acid graphene solution was 3:1.5:8. The mixture was stirred for another 3 hours and then cooled to 40°C. Sulfuric acid solution was then added dropwise to the reaction solution until the pH reached 5-6 and the mixture was stirred for half an hour. Sodium hydroxide solution was then added dropwise until the pH reached 10-11 and the mixture was stirred for another half hour. After the reaction was completed, the reaction product was washed with water at least three times and dried in a vacuum oven at 70°C for 8 hours to obtain modified graphene oxide.

[0051] The preparation method of the above-mentioned graphene-modified concrete material includes the following steps:

[0052] Step 1: Weigh each component according to the weight proportions, mix them into a cement mixer, and mix at a speed of 150 r / min for 15 min;

[0053] Step 2: Pour the well-mixed slurry from the mixer into the mold, vibrate to degas it, cover the mold with plastic film, keep it at room temperature for at least 24 hours, then demold it and cure it for 28 days at a temperature of 22±2℃ and a humidity of 90%±2% to obtain graphene-modified concrete material.

[0054] Example 2

[0055] A graphene-modified concrete material, comprising the following components by weight:

[0056] 100 parts cement, 132 parts coarse aggregate, 258 parts fine aggregate, 23 parts fly ash, 6 parts modified graphene oxide, 1.8 parts water-reducing agent, 5 parts polypropylene fiber and 65 parts water.

[0057] Wherein, the cement is P.O42.5 ordinary Portland cement; the coarse aggregate is pebbles with a particle size between 4.75-10mm; the fine aggregate is sea sand with a particle size between 0.15-4.75mm; and the fly ash is Grade I fly ash.

[0058] The water-reducing agent is a polycarboxylate high-efficiency water-reducing agent, including model SPC-100; the polypropylene fiber has a diameter of 20-30μm and a length of 15-30mm.

[0059] The method for preparing the modified graphene oxide includes:

[0060] S1, sulfonation treatment:

[0061] Weigh out p-aminobenzenesulfonic acid and a 5% sodium hydroxide solution, mix them, heat to 50°C, stir until dissolved and homogeneous, then cool to room temperature, add sodium nitrite (mass ratio of p-aminobenzenesulfonic acid, sodium nitrite, and sodium hydroxide solution is 1:0.3:4), stir thoroughly again to obtain mixture A; weigh out a 5% hydrochloric acid solution, place it in an ice-water bath, stir for half an hour, then add mixture A dropwise (mass ratio of hydrochloric acid solution to mixture A is 1.2:1), continue stirring for half an hour after the addition is complete, then filter and collect the precipitate to obtain solid B;

[0062] Solid B and deionized water were mixed and stirred thoroughly in an ice-water bath for half an hour. Then, graphene oxide (oxygen content 30%, purity >99%, particle size 1.5-3μm, thickness 1.5-2.2nm, number of layers 2-5) was added and stirred for another half hour. The mass ratio of solid B, graphene oxide and deionized water was 0.3:1:40. The precipitate was collected by filtration, washed with water at least three times, and dried to obtain sulfonated graphene.

[0063] S2, Polymerization Modification Reaction

[0064] Sulfonated graphene was mixed in deionized water at a mass ratio of 1:10. After thorough dispersion, a sulfonated graphene solution was obtained.

[0065] Sodium hydroxide solution was added dropwise to a 37% formaldehyde solution to maintain the pH of the mixture at 9-10. Melamine was then added, and the mixture was heated to 60°C and stirred for 20 minutes. Then, sulfonated graphene solution was slowly added. The mass ratio of formaldehyde solution, melamine, and sulfonated graphene solution was 2:1:6. The mixture was stirred for another 2 hours and then cooled to 35°C. Sulfuric acid solution was then added dropwise to the reaction solution until the pH reached 5-6 and the mixture was stirred for half an hour. Sodium hydroxide solution was then added dropwise until the pH reached 10-11 and the mixture was stirred for another half hour. After the reaction was completed, the reaction product was washed with water at least three times and dried in a vacuum oven at 60°C for 5 hours to obtain modified graphene oxide.

[0066] The preparation method of the above-mentioned graphene-modified concrete material includes the following steps:

[0067] Step 1: Weigh each component according to the weight proportions, mix them into a cement mixer, and mix at a speed of 100 r / min for 10 min;

[0068] Step 2: Pour the well-mixed slurry from the mixer into the mold, vibrate to degas it, cover the mold with plastic film, keep it at room temperature for at least 24 hours, then demold it and cure it for 28 days at a temperature of 22±2℃ and a humidity of 90%±2% to obtain graphene-modified concrete material.

[0069] Example 3

[0070] A graphene-modified concrete material, comprising the following components by weight:

[0071] 100 parts cement, 224 parts coarse aggregate, 386 parts fine aggregate, 46 parts fly ash, 12 parts modified graphene oxide, 3.6 parts water-reducing agent, 10 parts polypropylene fiber and 85 parts water.

[0072] Wherein, the cement is P.O42.5 ordinary Portland cement; the coarse aggregate is crushed stone or gravel with a particle size between 4.75-10mm; the fine aggregate is river sand or sea sand with a particle size between 0.15-4.75mm; and the fly ash is Grade I fly ash.

[0073] The water-reducing agent is a polycarboxylate superplasticizer, including model SPC-101; the polypropylene fiber has a diameter of 20-30μm and a length of 15-30mm.

[0074] The method for preparing the modified graphene oxide includes:

[0075] S1, sulfonation treatment:

[0076] Weigh out p-aminobenzenesulfonic acid and a 5% sodium hydroxide solution, mix them, heat to 60°C, stir until dissolved and homogeneous, then cool to room temperature, add sodium nitrite (mass ratio of p-aminobenzenesulfonic acid, sodium nitrite, and sodium hydroxide solution is 1:0.5:8), stir thoroughly again to obtain mixture A; weigh out a 5% hydrochloric acid solution, place it in an ice-water bath, stir for half an hour, then add mixture A dropwise (mass ratio of hydrochloric acid solution to mixture A is 1.6:1), continue stirring for half an hour after the addition is complete, then filter and collect the precipitate to obtain solid B;

[0077] Solid B and deionized water were mixed and stirred thoroughly in an ice-water bath for half an hour. Then, graphene oxide (oxygen content 30%, purity >99%, particle size 1.5-3μm, thickness 1.5-2.2nm, number of layers 2-5) was added and stirred for another half hour. The mass ratio of solid B, graphene oxide and deionized water was 0.6:1:60. The precipitate was collected by filtration, washed with water at least three times, and dried to obtain sulfonated graphene.

[0078] S2, Polymerization Modification Reaction

[0079] Sulfonated graphene was mixed in deionized water at a mass ratio of 1:20. After thorough dispersion, a sulfonated graphene solution was obtained.

[0080] Sodium hydroxide solution was added dropwise to a 37% formaldehyde solution to maintain the pH of the mixture at 9-10. Melamine was then added, and the mixture was heated to 70°C and stirred for 50 minutes. Then, sulfonated graphene solution was slowly added. The mass ratio of formaldehyde solution, melamine, and sulfonated graphene solution was 4:2:10. The mixture was stirred for another 4 hours and then cooled to 45°C. Sulfuric acid solution was then added dropwise to the reaction solution until the pH reached 5-6 and the mixture was stirred for half an hour. Sodium hydroxide solution was then added dropwise until the pH reached 10-11 and the mixture was stirred for another half hour. After the reaction was completed, the reaction product was washed with water at least three times and dried in a vacuum oven at 80°C for 10 hours to obtain modified graphene oxide.

[0081] The preparation method of the above-mentioned graphene-modified concrete material includes the following steps:

[0082] Step 1: Weigh each component according to the weight proportions, mix them into a cement mixer, and mix at a speed of 200 r / min for 20 min;

[0083] Step 2: Pour the well-mixed slurry from the mixer into the mold, vibrate to degas it, cover the mold with plastic film, keep it at room temperature for at least 24 hours, then demold it and cure it for 28 days at a temperature of 22±2℃ and a humidity of 90%±2% to obtain graphene-modified concrete material.

[0084] Comparative Example 1

[0085] A graphene-modified concrete material, which differs from Example 1 in that the modified graphene oxide in the composition is replaced with graphene oxide.

[0086] Comparative Example 2

[0087] A graphene-modified concrete material, which differs from Example 1 in that the modified graphene oxide in the composition is replaced with sulfonated graphene (for preparation details, please refer to step S1 of the preparation method of modified graphene oxide in Example 1).

[0088] Comparative Example 3

[0089] A graphene-modified concrete material differs from Example 1 in that the preparation method of the modified graphene oxide in its composition is different. The preparation method of the modified graphene oxide includes:

[0090] S1. Mix graphene in deionized water at a mass ratio of 1:15. After thorough dispersion, a graphene solution is obtained.

[0091] S2. Add sodium hydroxide solution dropwise to a 37% formaldehyde solution, maintaining the pH of the mixture at 9-10. Then add melamine, heat to 65℃, and stir for 30 minutes. Slowly add graphene solution, with a mass ratio of formaldehyde solution, melamine, and graphene solution of 3:1.5:8. Continue stirring for 3 hours, then cool to 40℃. First, add sulfuric acid solution dropwise to the reaction solution until the pH is 5-6, and stir for half an hour. Then add sodium hydroxide solution dropwise until the pH is 10-11, and stir for half an hour. After the reaction is complete, wash the reaction product with water at least three times and dry it in a vacuum oven at 70℃ for 8 hours to obtain modified graphene oxide.

[0092] Experimental Example

[0093] The graphene-modified concrete materials prepared in Example 1 and Comparative Examples 1-3 were tested as follows: the compressive strength and flexural strength were tested according to GB / T 50081-2016 "Standard for Test Methods of Mechanical Properties of Ordinary Concrete", and the impermeability and crack resistance were tested according to GB / T 50082-2009 "Standard for Test Methods of Long-Term Performance and Durability of Ordinary Concrete". The test results are shown in Table 1.

[0094] Table 1. Test results of different graphene-modified concrete materials

[0095]

[0096] As can be seen from Table 1, the compressive strength and flexural strength of the graphene-modified concrete material prepared in Example 1 of the present invention are much higher than those in Comparative Example 1, and the water seepage height after 28 days is lower and the total crack area is smaller, indicating that it has higher strength and toughness, and also has the advantages of being waterproof and not prone to cracking.

[0097] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. The illustrative expressions of the above terms in this specification should not be construed as necessarily referring to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. In addition, those skilled in the art can combine and integrate the different embodiments or examples described in this specification.

[0098] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A graphene-modified concrete material, characterized in that, Calculated by weight, it includes the following ingredients: 100 parts cement, 132-224 parts coarse aggregate, 258-386 parts fine aggregate, 23-46 parts fly ash, 6-12 parts modified graphene oxide, 1.8-3.6 parts water-reducing agent, 5-10 parts polypropylene fiber and 65-85 parts water; The method for preparing the modified graphene oxide includes: S1, sulfonation treatment: Weigh out p-aminobenzenesulfonic acid and sodium hydroxide solution, mix them, heat to 50-60℃, stir until dissolved and homogeneous, cool to room temperature, add sodium nitrite, stir thoroughly again to obtain mixture A; weigh out hydrochloric acid solution, place it in an ice-water bath, stir for half an hour, add mixture A dropwise, continue stirring for half an hour after the addition is complete, then filter and collect the precipitate to obtain solid B; Solid B and deionized water were mixed and stirred thoroughly in an ice-water bath for half an hour. Then graphene oxide was added and stirred for another half hour. The precipitate was collected by filtration, washed with water at least three times, and dried to obtain sulfonated graphene. S2, Polymerization Modification Reaction Sulfonated graphene was mixed in deionized water and dispersed thoroughly to obtain a sulfonated graphene solution. Add sodium hydroxide solution dropwise to formaldehyde solution to maintain the pH of the mixture at 9-10. Then add melamine, heat to 60-70℃, stir for 20-50 minutes, slowly add sulfonic acid graphene solution, continue stirring for 2-4 hours, cool to 35-45℃, and then carry out acid polymerization and basic polymerization reactions in sequence. After the reaction is completed, wash the reaction product with water at least three times and dry it in a vacuum chamber to obtain modified graphene oxide.

2. The graphene-modified concrete material according to claim 1, characterized in that, The cement is P.O42.5 ordinary Portland cement.

3. The graphene-modified concrete material according to claim 1, characterized in that, The coarse aggregate is crushed stone or pebbles with a particle size between 4.75 and 10 mm; the fine aggregate is river sand or sea sand with a particle size between 0.15 and 4.75 mm.

4. The graphene-modified concrete material according to claim 1, characterized in that, The fly ash is Class I fly ash; the water-reducing agent is a polycarboxylate high-efficiency water-reducing agent, including models SPC-100 or SPC-101; the polypropylene fiber has a diameter of 20-30μm and a length of 15-30mm.

5. The graphene-modified concrete material according to claim 1, characterized in that, In S1, the mass fraction of sodium hydroxide solution is 5%, and the mass ratio of p-aminobenzenesulfonic acid, sodium nitrite, and sodium hydroxide solution is 1:0.3-0.5:4-8.

6. The graphene-modified concrete material according to claim 1, characterized in that, In S1, the mass fraction of hydrochloric acid solution is 5%, and the mass ratio of hydrochloric acid solution to mixture A is 1.2-1.6:1; the mass ratio of solid B, graphene oxide and deionized water is 0.3-0.6:1:40-60.

7. The graphene-modified concrete material according to claim 1, characterized in that, In the S2 sulfonated graphene solution, the mass ratio of sulfonated graphene to deionized water is 1:10-20; the mass fraction of formaldehyde solution is 37%, and the mass ratio of formaldehyde solution, melamine and sulfonated graphene solution is 2-4:1-2:6-10.

8. The graphene-modified concrete material according to claim 1, characterized in that, In S2, the acidic polymerization reaction involves adding sulfuric acid solution dropwise to the reaction solution until the pH of the reaction solution is 5-6, and stirring for half an hour; the alkaline polymerization reaction involves adding sodium hydroxide solution dropwise to the reaction solution after the acidic polymerization reaction until the pH of the reaction solution is 10-11, and stirring for half an hour.

9. A method for preparing the graphene-modified concrete material according to claim 1, characterized in that, Includes the following steps: Step 1: Weigh out each component according to the weight proportions, mix them into a cement mixer, and mix at a speed of 100-200 r / min for 10-20 min; Step 2: Pour the well-mixed slurry from the mixer into the mold, vibrate to degas it, cover the mold with plastic film, keep it at room temperature for at least 24 hours, then demold it and cure it for 14-28 days at a temperature of 22±2℃ and a humidity of 90%±2% to obtain graphene-modified concrete material.

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