High-strength corrosion-resistant structural steel material and preparation method thereof

Abstract

The invention discloses a high-strength corrosion-resistant structural steel material and a preparation method thereof, belongs to the technical field of structural steel preparation, and aims to solve the technical problem that the mechanical property and the corrosion resistance of the structural steel material need to be further improved in the prior art. The hybrid film forming liquid serves as a continuous phase, the cerium modified corrosion inhibition filler is introduced to the side close to the steel substrate, the molybdenum modified barrier filler is introduced to the surface layer area, a composite protection system with division of labor in the thickness direction is constructed, and the scheme can achieve cooperation and unification of the stable interface of the steel substrate, the compact in-layer structure and surface layer medium barrier; therefore, the adhesion stability, the corrosion resistance and the overall structure retentivity in the service process of the high-strength corrosion-resistant structural steel material are improved.

Description

Technical Field

[0001] This invention relates to the field of structural steel preparation technology, specifically to a high-strength, corrosion-resistant structural steel material and its preparation method. Background Technology

[0002] In existing technologies, high-strength structural steel has been widely used in engineering equipment, transportation, energy facilities, and building components to balance load-bearing capacity and lightweight requirements. To address the issue of its susceptibility to corrosion from moisture, oxygen, and salt media in its service environment, surface protection methods are typically used to improve its corrosion resistance. For example, organic coatings, inorganic conversion films, zinc-rich primers, anti-rust pigment and filler systems, or composite protective coatings are applied to the surface of the steel substrate. These are combined with epoxy resin, silane, lamellar fillers, and corrosion inhibitors to construct a protective layer, aiming to form a protective structure on the substrate surface that isolates the media and slows down the corrosion process.

[0003] However, in existing high-strength structural steel protection systems, many solutions focus more on a single barrier or a single corrosion inhibition effect. The functional allocation in the coating thickness direction is not clear enough, resulting in the area near the steel substrate and the area far from the steel substrate often playing similar roles. The interface transition layer lacks targeted adjustment. As a result, after long-term penetration of external media, the steel substrate-coating interface is prone to become a preferential instability area, showing a tendency to local activation, decreased adhesion, and spread along the interface. Consequently, the corrosion inhibition effect is difficult to maintain at key interface positions, resulting in insufficient overall durability of the protective layer.

[0004] In addition, although some existing protective materials introduce lamellar fillers or inorganic functional particles to improve the barrier effect, the compatibility, dispersion stability and intralayer synergy between the filler and the film-forming system are still insufficient. This can easily lead to problems such as agglomeration, local looseness or discontinuous and uncontrolled mass transfer channels in the film. Especially when high-strength structural steel is simultaneously subjected to mechanical loads and the coupling effect of corrosive media, if the coating lacks a synergistic structure that combines interface stability, intralayer density and surface barrier, it is easy for micro-defects to expand during service, making it difficult to balance corrosion resistance and overall structural integrity.

[0005] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a high-strength, corrosion-resistant structural steel material and its preparation method, in order to solve the technical problem that the mechanical properties and corrosion resistance of existing structural steel materials need to be further improved.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A method for preparing a high-strength, corrosion-resistant structural steel material includes the following steps:

[0009] S1. The composite steel substrate is added to the melting furnace and heated and melted under nitrogen. After the melt is uniform, it is poured into the mold to form a steel billet. After natural cooling and demolding, a high-strength structural steel substrate is obtained.

[0010] S2. Cerium-modified corrosion inhibitor filler and hybrid film-forming liquid are added to the reaction vessel and stirred until evenly dispersed to obtain the bottom coating liquid. The bottom coating liquid is then coated on the surface of the high-strength structural steel substrate, and post-treatment is performed to obtain the interfacial corrosion inhibitor layer structural steel substrate.

[0011] S3. Molybdenum-modified barrier filler and hybrid film-forming liquid are added to the reaction vessel and stirred until evenly dispersed to obtain a surface coating liquid. The surface coating liquid is then coated on the surface of the interfacial corrosion inhibitor structural steel substrate, and post-treatment is performed to obtain high-strength corrosion-resistant structural steel material.

[0012] Further, in step S1, the composite steel substrate is obtained by mixing iron, graphite, manganese, silicon, chromium, nickel, copper, molybdenum, niobium and titanium in a ratio of 1900-1920g:1-2g:24-32g:5-6g:10-12g:8-10g:6-8g:3-5g:1g:1g. The post-processing includes: heating the steel billet to 900-940℃ and holding it for 35-55min, then quenching it, followed by tempering it at 430-470℃ for 45-75min, and cooling it to obtain a high-strength structural steel matrix.

[0013] Furthermore, in step S2, the ratio of the cerium-modified corrosion inhibitor filler to the hybrid film-forming liquid is 2-3g:100mL, wherein the dry film thickness of the bottom coating liquid is 8-12μm, and the post-treatment includes: pre-curing at 75-85℃ for 15-25min to obtain an interface corrosion inhibitor layer structure steel substrate.

[0014] Furthermore, in step S3, the ratio of the molybdenum-modified barrier filler to the hybrid film-forming liquid is 0.2-0.4g:100mL, wherein the dry film thickness of the surface coating liquid is 18-24μm, and the post-treatment includes: curing at 110-130℃ for 50-70min, and then placing at room temperature for 20-28h to obtain high-strength corrosion-resistant structural steel material.

[0015] Furthermore, the cerium-modified corrosion inhibitor filler is prepared by the following method:

[0016] A1. Add the tungstate mixture to the reactor, then add the metal salt mixture dropwise while controlling the reactor temperature at 60-70℃ and the pH of the reaction system at 9.5-10.2. After the addition is complete, continue to keep the mixture warm and stir for 6-8 hours. The zinc aluminum tungstate precursor is then obtained through post-processing.

[0017] A2. Add zinc aluminum tungstate precursor and deionized water to the reactor and stir until uniform. Then add cerium nitrate hexahydrate and stir until uniform. Next, add 30 wt% hydrogen peroxide solution and adjust the pH of the reaction system to 8.3-8.8 with 25-28 wt% ammonia. Then heat the reactor to 35-45℃ and keep it at that temperature for 2-4 hours. The post-treatment yields cerium-modified corrosion inhibitor filler.

[0018] Further, in step A1, the metal salt mixture is obtained by mixing zinc nitrate hexahydrate, aluminum nitrate nonahydrate, and deionized water in a ratio of 16-18g:5-8g:120mL; the tungstate mixture is obtained by mixing sodium tungstate dihydrate, sodium hydroxide, and deionized water in a ratio of 7-9g:8-10g:160mL. The post-treatment includes: after the reaction is completed, filtering to collect the filter cake and washing it until neutral, then drying it to constant weight to obtain zinc aluminum tungstate precursor;

[0019] Furthermore, in step A1, the metal salt mixture and the tungstate mixture are mixed at a volume ratio of 5 mL: 6-7 mL, and the addition time is 2-3 h.

[0020] Further, in step A2, the ratio of the zinc aluminum tungstic acid precursor, deionized water, cerium nitrate hexahydrate and 30 wt% hydrogen peroxide solution is 21-27 g: 500 mL: 9-12 g: 1-2 mL. The post-treatment includes: after the reaction is completed, filtering to collect the filter cake and washing it to neutral, then drying it to constant weight to obtain cerium-modified corrosion inhibitor filler.

[0021] Furthermore, the molybdenum-modified barrier filler is prepared by the following method:

[0022] B1. Add graphene oxide and 1.5wt% hydrochloric acid aqueous solution to the reaction vessel and stir until evenly dispersed. Then add aniline and m-aminobenzenesulfonic acid. Subsequently, cool the reaction vessel to 0-5℃ and add 10wt% ammonium persulfate aqueous solution dropwise. After the addition is completed, continue to keep it at 0-5℃ and stir for 5-7 hours. The post-processing yields polyaniline graphene precursor.

[0023] B2. Add polyaniline graphene precursor, anhydrous ethanol and deionized water to the reaction vessel and stir until uniformly mixed. Then add ammonium heptamolybdate tetrahydrate and glacial acetic acid to adjust the pH of the reaction system to 4.0-4.5. Then heat the reaction vessel to 35-45℃ and keep it at that temperature for 2-3 hours. The post-treatment yields molybdenum modified barrier filler.

[0024] Further, in step B1, the ratio of graphene oxide, 1.5 wt% hydrochloric acid aqueous solution, aniline, m-aminobenzenesulfonic acid and 10 wt% ammonium persulfate aqueous solution is 2-3 g: 500 mL: 2-3 g: 4-5 g: 40-60 mL. The post-processing includes: after the reaction is completed, filtering to collect the filter cake and washing it to neutral, then drying it to constant weight to obtain polyaniline graphene precursor;

[0025] Furthermore, in step B2, the ratio of the polyaniline graphene precursor, anhydrous ethanol, deionized water, and ammonium heptamolybdate tetrahydrate is 9-10g:100mL:100mL:3-4g. The post-treatment includes: after the reaction is completed, filtering to collect the filter cake and washing it to neutral, then drying it to constant weight to obtain the molybdenum modified barrier packing.

[0026] Furthermore, the preparation method of the hybrid film-forming solution is as follows: anhydrous ethanol, deionized water and glacial acetic acid are added to a reaction vessel and stirred evenly, then 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane and tetraethyl orthosilicate are added in sequence and stirred, then bisphenol A type epoxy resin is added, and the mixture is stirred and dispersed for 30-50 minutes. After standing and degassing, the hybrid film-forming solution is obtained.

[0027] Furthermore, in the preparation of the hybrid film-forming solution, the ratio of anhydrous ethanol, deionized water, glacial acetic acid, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, tetraethyl orthosilicate, and bisphenol A epoxy resin is 40 mL:10 mL:1 mL:4-6 mL:2-3 mL:4-5 mL:50 g, and the hybrid film-forming solution needs to be used within 4-6 hours.

[0028] The present invention also discloses a high-strength, corrosion-resistant structural steel material, which is prepared by a method for preparing high-strength, corrosion-resistant structural steel materials.

[0029] The present invention has the following beneficial effects:

[0030] 1. The hybrid film-forming liquid prepared by this invention forms a continuous organic-inorganic hybrid layer on the surface of a steel substrate after curing. This layer provides a relatively complete coverage of the substrate surface and makes the structural transition of the surface area smoother. Therefore, it is not easy for stress abrupt changes caused by local defects to occur under external load. Among them, the cerium-modified corrosion inhibitor is disposed on the side close to the steel substrate. Its presence in the interface area makes the bottom layer state more stable and can reduce the interference of environmental factors on the continuity of surface stress. The molybdenum-modified barrier filler is distributed on the outer layer, which further maintains the integrity and density of the coating surface. Thus, the hybrid film-forming liquid, cerium-modified corrosion inhibitor, and molybdenum-modified barrier filler form a continuous combination from the inside to the outside in the thickness direction. Under room temperature tensile and impact loads, the material maintains a relatively coordinated correspondence between surface constraint, interface stability, and outer layer integrity. The corresponding deformation and load-bearing processes thus exhibit a relatively stable state.

[0031] 2. The cerium-modified corrosion inhibitor filler prepared in this invention is located in the interface region near the steel substrate. When the corrosive medium enters the system, the first key part it contacts is not the exposed metal surface, but the interface layer regulated by the underlying functional phase. This configuration makes the evolution process of the interface region in the salt spray environment more hierarchical. The hybrid film-forming liquid forms a continuous network in the middle, providing a carrying and fixing space for the underlying corrosion inhibitor components, so that the region does not become a permeation channel prematurely due to local looseness. After the molybdenum-modified barrier filler is placed in the outer layer, the migration path of water, oxygen and corrosive ions becomes more tortuous. In this way, the outer layer barrier, network delay and interface regulation are connected in space in sequence. The transmission process of the corrosive medium from the surface to the inside is no longer a single and direct through-through mode. The state changes between the material surface, interface and substrate under neutral salt spray conditions are also more moderate.

[0032] 3. The molybdenum-modified barrier filler prepared by this invention, after entering the surface system, does not only serve as an outer layer shield. When it is cured together with the hybrid film-forming liquid, it forms a relatively continuous composite phase structure inside the surface layer, thereby enabling the upper coating to maintain a relatively complete integrity when subjected to external forces or environmental disturbances. After the hybrid film-forming liquid is located in the intermediate transition layer, it not only forms sufficient contact with the steel substrate surface, but also provides a continuous connecting matrix for the two types of functional fillers, so that the difference in interlayer properties does not directly transform into abrupt interface changes. Furthermore, after the cerium-modified corrosion inhibitor filler is further arranged on the side closer to the steel substrate, the bottom layer area can still maintain a relatively stable adhesion state under long-term environmental action. Thus, the continuity of the outer layer structure, the transition of the intermediate network, and the stability of the bottom layer interface unfold sequentially within the same system. Under tensile load, the force transmission between each layer tends to be more consistent, and the interface is less likely to show obvious early loosening or concentrated instability. Attached Figure Description

[0033] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 SEM image of the cerium-modified corrosion inhibitor prepared in Example 3;

[0035] Figure 2 The image shows a SEM image of the molybdenum-modified barrier filler prepared in Example 6. Detailed Implementation

[0036] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] In this application, the graphene oxide used was purchased from Shanghai Maclean Biotechnology Co., Ltd., with the product number G768901; the bisphenol A type epoxy resin used was purchased from Shanghai Maclean Biotechnology Co., Ltd., with the product number B665331.

[0038] Example 1

[0039] This embodiment provides a method for preparing cerium-modified corrosion inhibitor filler, including the following steps:

[0040] Step I: Preparation of zinc aluminum tungstate precursor

[0041] Weigh out 16.0 g of zinc nitrate hexahydrate, 5.0 g of aluminum nitrate nonahydrate, and 120.0 mL of deionized water and mix them to obtain a metal salt mixture.

[0042] Weigh out 7.0 g of sodium tungstate dihydrate, 8.0 g of sodium hydroxide and 160.0 mL of deionized water and mix them to obtain a tungstate mixture;

[0043] Weigh 120.0 mL of tungstate mixture and add it to the reaction vessel. Then, add 100.0 mL of metal salt mixture dropwise while controlling the reaction vessel temperature at 60℃ and the pH of the reaction system at 9.5. The dropwise addition time is 2 h. After the dropwise addition is completed, continue to keep warm and stir for 6 h. After the reaction is completed, filter and collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain zinc aluminum tungstate precursor.

[0044] Step II: Preparation of cerium-modified corrosion inhibitor filler

[0045] Weigh 21.0g of zinc aluminum tungstic acid precursor and 500.0mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous, then add 9.0g of cerium nitrate hexahydrate and stir until homogeneous. Then add 1.0mL of 30wt% hydrogen peroxide solution and adjust the pH of the reaction system to 8.3 with 25wt% ammonia. Then heat the reaction vessel to 35℃ and keep it at that temperature for 2h with stirring. After the reaction is complete, filter and collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain cerium-modified corrosion inhibitor filler.

[0046] The reaction principle for preparing cerium-modified corrosion inhibitor fillers is as follows:

[0047] Under alkaline conditions, metal ions in zinc and aluminum salts react with tungsten-containing anions in the tungstate system to form a complex precipitation, resulting in precursor particles mainly composed of zinc, aluminum, and tungsten oxoacid salts. Further introduction of cerium salts... 3+ In a weakly alkaline medium, hydrolysis occurs to a certain extent, and oxygen-containing cerium species are formed under the action of hydrogen peroxide. These species can be deposited or bound to the surface of precursor particles, and adsorption, coordination or condensation occur between them and the surface hydroxyl groups, metal-oxygen structures and local tungsten-containing groups, thereby introducing the cerium component into the zinc aluminum tungstic acid precursor system to obtain cerium-modified corrosion inhibitor filler.

[0048] The working principle of cerium-modified corrosion inhibitors in high-strength, corrosion-resistant structural steel is as follows:

[0049] The zinc aluminum tungstate precursor prepared in step I provides an inorganic functional phase basis with multi-metal-oxygen framework characteristics for the system. In the hybrid film-forming system, it serves as a dispersion framework to improve the compactness of the coating microstructure and the tortuosity of the mass transfer path. On the other hand, it serves as a carrier for subsequent functional components, which is conducive to establishing a relatively stable underlying structure in the region close to the steel substrate. The cerium-modified corrosion inhibitor prepared in step II further endows the particles with interface regulation function and environmental response stability on the basis of the precursor, making it easier to form a continuous transition region between the steel substrate and the underlying coating. It also inhibits the interface activation, local instability and the process of expansion along the interface. Thus, the former mainly corresponds to the establishment of the structural framework and barrier base, while the latter mainly corresponds to the enhancement of interface stability and corrosion inhibition function. The combined effect of the two is conducive to the formation of a relatively complete system support for the final high-strength corrosion-resistant structural steel material in terms of adhesion state, resistance to media penetration, long-term corrosion resistance retention and structural coordination during mechanical service.

[0050] Example 2

[0051] This embodiment provides a method for preparing cerium-modified corrosion inhibitor filler, including the following steps:

[0052] Step I: Preparation of zinc aluminum tungstate precursor

[0053] Weigh out 18.0 g of zinc nitrate hexahydrate, 8.0 g of aluminum nitrate nonahydrate, and 120.0 mL of deionized water and mix them to obtain a metal salt mixture.

[0054] Weigh out 9.0 g of sodium tungstate dihydrate, 10.0 g of sodium hydroxide and 160.0 mL of deionized water and mix them to obtain a tungstate mixture;

[0055] Weigh 140.0 mL of tungstate mixture and add it to the reactor. Then add 100.0 mL of metal salt mixture dropwise while controlling the reactor temperature at 70 °C and the pH of the reaction system at 10.2. The dropwise addition time is 3 h. After the dropwise addition is completed, continue to keep warm and stir for 8 h. After the reaction is completed, filter and collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain zinc aluminum tungstate precursor.

[0056] Step II: Preparation of cerium-modified corrosion inhibitor filler

[0057] Weigh 27.0g of zinc aluminum tungstic acid precursor and 500.0mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous, then add 12.0g of cerium nitrate hexahydrate and stir until homogeneous. Then add 2.0mL of 30wt% hydrogen peroxide solution and adjust the pH of the reaction system to 8.8 with 28wt% ammonia. Then heat the reaction vessel to 45℃ and keep it at that temperature with stirring for 4h. After the reaction is complete, filter and collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain cerium-modified corrosion inhibitor filler.

[0058] Example 3

[0059] This embodiment provides a method for preparing cerium-modified corrosion inhibitor filler, including the following steps:

[0060] Step I: Preparation of zinc aluminum tungstate precursor

[0061] Weigh out 17.0 g of zinc nitrate hexahydrate, 6.5 g of aluminum nitrate nonahydrate, and 120.0 mL of deionized water and mix them to obtain a metal salt mixture.

[0062] Weigh out 8.0 g of sodium tungstate dihydrate, 9.0 g of sodium hydroxide and 160.0 mL of deionized water and mix them to obtain a tungstate mixture;

[0063] Weigh 130.0 mL of tungstate mixture and add it to the reaction vessel. Then, add 100.0 mL of metal salt mixture dropwise while controlling the reaction vessel temperature at 65℃ and the pH of the reaction system at 9.9. The dropwise addition time is 3 h. After the dropwise addition is completed, continue to keep warm and stir for 7 h. After the reaction is completed, filter and collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain zinc aluminum tungstate precursor.

[0064] Step II: Preparation of cerium-modified corrosion inhibitor filler

[0065] Weigh 24.0g of zinc aluminum tungstic acid precursor and 500.0mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous, then add 10.5g of cerium nitrate hexahydrate and stir until homogeneous. Then add 1.5mL of 30wt% hydrogen peroxide solution and adjust the pH of the reaction system to 8.6 with 26wt% ammonia. Then heat the reaction vessel to 40℃ and keep it at that temperature for 3h with stirring. After the reaction is complete, filter and collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain cerium-modified corrosion inhibitor filler.

[0066] Example 4

[0067] This embodiment provides a method for preparing molybdenum-modified barrier fillers, including the following steps:

[0068] Step ①: Preparation of polyaniline-graphene precursor

[0069] Weigh 2.0 g of graphene oxide and 500.0 mL of 1.5 wt% hydrochloric acid aqueous solution and add them to the reaction vessel. Stir until the mixture is evenly dispersed. Then add 2.0 g of aniline and 4.0 g of m-aminobenzenesulfonic acid. Cool the reaction vessel to 0 °C and add 40.0 mL of 10 wt% ammonium persulfate aqueous solution dropwise. After the addition is complete, continue stirring at 0 °C for 5 h. After the reaction is complete, filter to collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain polyaniline graphene precursor.

[0070] Step 2: Preparation of molybdenum-modified barrier filler

[0071] Weigh out 9.0 g of polyaniline graphene precursor, 100.0 mL of anhydrous ethanol and 100.0 mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous, then add 3.0 g of ammonium heptamolybdate tetrahydrate and glacial acetic acid to adjust the pH of the reaction system to 4.0. Then heat the reaction vessel to 35 °C and keep it at that temperature for 2 h with stirring. After the reaction is complete, filter the filter cake and wash it until neutral. Then dry it to constant weight to obtain molybdenum modified barrier filler.

[0072] The reaction principle for preparing molybdenum-modified barrier fillers is as follows:

[0073] In an acidic dispersion system, aniline and m-aminobenzenesulfonic acid undergo oxidative polymerization initiated by ammonium persulfate to form polyaniline-like substances containing conjugated chain structures. The oxygen-containing functional groups such as hydroxyl, epoxy, and carboxyl groups on the surface of graphene oxide can generate hydrogen bonding, electrostatic interaction, and π-π interaction with the polymerization products, so that the polyaniline component is loaded on the surface of the graphene sheets. After the introduction of ammonium heptamolybdate, the molybdate species can undergo adsorption, association, or coordination with the nitrogen-containing groups in the polyaniline chain segments and the oxygen-containing functional groups on the graphene surface under weakly acidic conditions, so that the molybdenum component is combined in the polyaniline / graphene composite system to obtain molybdenum-modified barrier filler.

[0074] The working principle of molybdenum-modified barrier fillers in high-strength, corrosion-resistant structural steel materials is as follows:

[0075] In this process, the polyaniline-graphene precursor obtained in step ① is essentially a composite functional phase with the synergistic characteristics of a sheet barrier framework and conductive conjugated segments. On the one hand, it relies on the high aspect ratio structure of the graphene sheets to extend the migration paths of moisture, oxygen, and corrosive ions in the coating. On the other hand, it uses the polyaniline component to improve its compatibility and dispersion stability with the hybrid film-forming system, thereby facilitating the formation of a continuous and relatively dense surface structure. The molybdenum-modified barrier filler obtained in step ② further introduces molybdenum functional sites on the basis of the precursor, so that the composite particles retain both sheet barrier and network characteristics. In addition to densification, it also has stronger interfacial association and structural stability under environmental disturbances, which is more conducive to maintaining surface integrity, slowing down the penetration and expansion of the medium from the surface to the interior, and reducing the tendency of local loose areas to evolve into unstable defects. Thus, the former mainly corresponds to the establishment of the surface barrier skeleton and the foundation of the conductive network, while the latter mainly corresponds to the further enhancement of the outer barrier function and structural stability. The combined effect of the two is conducive to maintaining a superior level of high-strength corrosion-resistant structural steel materials in terms of neutral salt spray corrosion resistance time, adhesion state, and overall structural coordination during service.

[0076] Example 5

[0077] This embodiment provides a method for preparing molybdenum-modified barrier fillers, including the following steps:

[0078] Step ①: Preparation of polyaniline-graphene precursor

[0079] Weigh out 3.0 g of graphene oxide and 500.0 mL of 1.5 wt% hydrochloric acid aqueous solution and add them to the reaction vessel. Stir until the mixture is evenly dispersed. Then add 3.0 g of aniline and 5.0 g of m-aminobenzenesulfonic acid. Then cool the reaction vessel to 5 °C and add 60.0 mL of 10 wt% ammonium persulfate aqueous solution dropwise. After the addition is complete, continue to stir at 5 °C for 7 h. After the reaction is complete, filter to collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain polyaniline graphene precursor.

[0080] Step 2: Preparation of molybdenum-modified barrier filler

[0081] Weigh out 10.0 g of polyaniline graphene precursor, 100.0 mL of anhydrous ethanol and 100.0 mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous, then add 4.0 g of ammonium heptamolybdate tetrahydrate and glacial acetic acid to adjust the pH of the reaction system to 4.5. Then heat the reaction vessel to 45 °C and keep it at that temperature for 3 h with stirring. After the reaction is complete, filter the filter cake and wash it until neutral. Then dry it to constant weight to obtain molybdenum modified barrier filler.

[0082] Example 6

[0083] This embodiment provides a method for preparing molybdenum-modified barrier fillers, including the following steps:

[0084] Step ①: Preparation of polyaniline-graphene precursor

[0085] Weigh 2.5g of graphene oxide and 500.0mL of 1.5wt% hydrochloric acid aqueous solution and add them to the reaction vessel. Stir until the mixture is evenly dispersed. Then add 2.5g of aniline and 4.5g of m-aminobenzenesulfonic acid. Cool the reaction vessel to 3℃ and add 50.0mL of 10wt% ammonium persulfate aqueous solution dropwise. After the addition is complete, continue stirring at 3℃ for 6 hours. After the reaction is complete, filter and collect the filter cake and wash it until neutral. Then dry it to constant weight to obtain polyaniline graphene precursor.

[0086] Step 2: Preparation of molybdenum-modified barrier filler

[0087] Weigh out 9.5g of polyaniline graphene precursor, 100.0mL of anhydrous ethanol and 100.0mL of deionized water and add them to the reaction vessel. Stir until the mixture is homogeneous, then add 3.5g of ammonium heptamolybdate tetrahydrate and glacial acetic acid to adjust the pH of the reaction system to 4.3. Then heat the reaction vessel to 40℃ and keep it at that temperature for 3 hours with stirring. After the reaction is complete, filter the filter cake and wash it until it is neutral. Then dry it to constant weight to obtain molybdenum modified barrier filler.

[0088] Example 7

[0089] This embodiment provides a method for preparing high-strength, corrosion-resistant structural steel material, including the following steps:

[0090] Step 1: Preparation of hybrid film-forming solution

[0091] Weigh out 200.0 mL of anhydrous ethanol, 50.0 mL of deionized water and 5.0 mL of glacial acetic acid and add them to the reaction vessel and stir until homogeneous. Then add 20.0 mL of 3-glycidoxypropyltrimethoxysilane, 10.0 mL of 3-aminopropyltriethoxysilane and 20.0 mL of tetraethyl orthosilicate and stir. Then add 250.0 g of bisphenol A epoxy resin and continue stirring and dispersing for 30 min. After standing to remove bubbles, the hybrid film-forming solution is obtained.

[0092] The reaction principle for preparing hybrid film-forming solutions is as follows:

[0093] In an aqueous alcohol solvent system, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and tetraethyl orthosilicate undergo hydrolysis to generate silanol intermediates. The generated silanols further undergo condensation reactions to form an inorganic network structure characterized by Si-O-Si bonds. At the same time, the organic functional groups in the silane components can undergo chemical reactions or intermolecular interactions with the bisphenol A type epoxy resin molecular chains, allowing the inorganic silicon-oxygen network and the organic resin to interpenetrate and form a relatively stable organic-inorganic hybrid system. Glacial acetic acid is mainly used to adjust the acidity of the system and promote the silane hydrolysis and condensation process.

[0094] The working principle of hybrid film-forming solutions in high-strength, corrosion-resistant structural steel materials is as follows:

[0095] The hybrid film-forming liquid obtained in this process is essentially a film-forming base system that combines the characteristics of an organic resin continuous phase and an inorganic silicon-oxygen network. Its structural origin determines that it is not a single resin binder phase, but rather a composite continuous structure that, after curing, forms an interpenetrating organic chain segment and Si-O-Si network. In the entire coating system, this hybrid film-forming liquid serves as a carrier and dispersion medium for two types of functional fillers, enabling the cerium-modified corrosion inhibitor and the molybdenum-modified barrier filler to maintain good embedding and interfacial bonding in their respective regions. Furthermore, the resulting... The organic-inorganic synergistic network endows the coating with better density, continuity and structural integrity, which helps to reduce the probability of formation of pores, microcracks and local phase separation defects. Thus, the film-forming liquid mainly plays the basic role of continuous film formation, intralayer connection, interface transition and stress coordination in the final high-strength corrosion-resistant structural steel material. It enables the bottom layer corrosion inhibition function and the outer layer barrier function to be stably integrated into the same film system, and further supports the adhesion state, media penetration resistance, corrosion resistance retention and overall structural stability during service.

[0096] Step 2: Preparation of high-strength structural steel matrix

[0097] Weigh out 1900.0g iron, 1.0g graphite, 24.0g manganese, 5.0g silicon, 10.0g chromium, 8.0g nickel, 6.0g copper, 3.0g molybdenum, 1.0g niobium and 1.0g titanium and mix them to obtain a composite steel substrate;

[0098] The composite steel substrate is added to a melting furnace and heated and melted under nitrogen. After the melt is homogeneous, it is poured into a mold to form a steel billet. After natural cooling and demolding, the steel billet is heated to 900℃ and held for 35 minutes before quenching. Then it is tempered at 430℃ for 45 minutes and cooled to obtain a high-strength structural steel substrate.

[0099] Step 3: Preparation of the interfacial corrosion-inhibiting layer structured steel substrate

[0100] Weigh 2.0g of the cerium-modified corrosion inhibitor prepared in Example 1 and 100.0mL of hybrid film-forming liquid and add them to the reaction vessel and stir evenly to obtain the bottom coating liquid; then coat the bottom coating liquid onto the surface of the high-strength structural steel substrate and pre-cur it at 75℃ for 15min to obtain a dry film with a thickness of 8μm, thus obtaining the interfacial corrosion inhibitor layer structural steel substrate.

[0101] Step 4: Preparation of high-strength, corrosion-resistant structural steel materials

[0102] Weigh 0.2g of the molybdenum-modified barrier filler prepared in Example 4 and 100.0mL of hybrid film-forming liquid and add them to the reaction vessel and stir evenly to obtain a surface coating liquid; then coat the surface coating liquid onto the surface of the interfacial corrosion inhibitor layer structural steel substrate and cure it at 110℃ for 50min, and then place it at room temperature for 20h to obtain a dry film with a thickness of 18μm, thus obtaining a high-strength corrosion-resistant structural steel material.

[0103] The reaction principle for preparing high-strength, corrosion-resistant structural steel materials is as follows:

[0104] In the smelting system, Fe forms a multi-element alloy system with C, Mn, Si, Cr, Ni, Cu, Mo, Nb, and Ti. During casting and subsequent quenching and tempering, metallurgical processes such as solid solution, phase transformation, and precipitation occur, resulting in a high-strength structural steel matrix. After dispersing cerium-modified corrosion inhibitors and molybdenum-modified barrier fillers in a hybrid film-forming liquid, the hydroxyl groups, metal oxygen structures, and nitrogen-containing groups in the polyaniline segments on the filler surface can undergo adsorption, hydrogen bonding, coordination, or interfacial association with the hybrid film-forming system. After coating and curing, the silicon-oxygen network, epoxy resin phase, and inorganic / organic composite fillers together constitute a composite coating structure bonded to the surface of the steel matrix, thereby obtaining a high-strength, corrosion-resistant structural steel material.

[0105] Example 8

[0106] This embodiment provides a method for preparing high-strength, corrosion-resistant structural steel material, including the following steps:

[0107] Step 1: Preparation of hybrid film-forming solution

[0108] Weigh out 200.0 mL of anhydrous ethanol, 50.0 mL of deionized water and 5.0 mL of glacial acetic acid and add them to the reaction vessel and stir until homogeneous. Then add 30.0 mL of 3-glycidoxypropyltrimethoxysilane, 15.0 mL of 3-aminopropyltriethoxysilane and 25.0 mL of tetraethyl orthosilicate and stir. Then add 250.0 g of bisphenol A epoxy resin and continue stirring and dispersing for 50 min. After standing to remove bubbles, the hybrid film-forming solution is obtained.

[0109] Step 2: Preparation of high-strength structural steel matrix

[0110] Weigh out 1920.0g iron, 2.0g graphite, 32.0g manganese, 6.0g silicon, 12.0g chromium, 10.0g nickel, 8.0g copper, 5.0g molybdenum, 1.0g niobium and 1.0g titanium and mix them to obtain a composite steel substrate;

[0111] The composite steel substrate is added to the melting furnace and heated and melted under nitrogen. After the melt is uniform, it is poured into the mold to form a steel billet. After natural cooling and demolding, the steel billet is heated to 940℃ and held for 55 minutes before quenching. Then it is tempered at 470℃ for 75 minutes and cooled to obtain a high-strength structural steel substrate.

[0112] Step 3: Preparation of the interfacial corrosion-inhibiting layer structured steel substrate

[0113] Weigh 3.0g of the cerium-modified corrosion inhibitor prepared in Example 2 and 100.0mL of the hybrid film-forming liquid and add them to the reaction vessel and stir evenly to obtain the bottom coating liquid; then coat the bottom coating liquid onto the surface of the high-strength structural steel substrate and pre-cur it at 85℃ for 25min to obtain a dry film with a thickness of 12μm, thus obtaining the interfacial corrosion inhibitor layer structural steel substrate.

[0114] Step 4: Preparation of high-strength, corrosion-resistant structural steel materials

[0115] Weigh 0.4g of the molybdenum-modified barrier filler prepared in Example 5 and 100.0mL of hybrid film-forming liquid and add them to the reaction vessel and stir evenly to obtain a surface coating liquid; then coat the surface coating liquid onto the surface of the interfacial corrosion inhibitor layer structural steel substrate and cure it at 130℃ for 70min, and then place it at room temperature for 28h to obtain a dry film with a thickness of 24μm, thus obtaining a high-strength corrosion-resistant structural steel material.

[0116] Example 9

[0117] This embodiment provides a method for preparing high-strength, corrosion-resistant structural steel material, including the following steps:

[0118] Step 1: Preparation of hybrid film-forming solution

[0119] Weigh out 200.0 mL of anhydrous ethanol, 50.0 mL of deionized water and 5.0 mL of glacial acetic acid and add them to the reaction vessel and stir until homogeneous. Then add 25.0 mL of 3-glycidyloxypropyltrimethoxysilane, 13.0 mL of 3-aminopropyltriethoxysilane and 23.0 mL of tetraethyl orthosilicate and stir. Then add 250.0 g of bisphenol A epoxy resin and continue stirring and dispersing for 40 min. After standing to remove bubbles, the hybrid film-forming solution is obtained.

[0120] Step 2: Preparation of high-strength structural steel matrix

[0121] Weigh out 1910.0g iron, 1.5g graphite, 28.0g manganese, 5.5g silicon, 11.0g chromium, 9.0g nickel, 7.0g copper, 4.0g molybdenum, 1.0g niobium and 1.0g titanium and mix them to obtain a composite steel substrate;

[0122] The composite steel substrate is added to a melting furnace and heated and melted under nitrogen. After the melt is homogeneous, it is poured into a mold to form a steel billet. After natural cooling and demolding, the steel billet is heated to 920℃ and held for 45 minutes before quenching. Then it is tempered at 450℃ for 60 minutes and cooled to obtain a high-strength structural steel substrate.

[0123] Step 3: Preparation of the interfacial corrosion-inhibiting layer structured steel substrate

[0124] Weigh 2.5g of the cerium-modified corrosion inhibitor prepared in Example 3 and 100.0mL of hybrid film-forming liquid and add them to the reaction vessel and stir evenly to obtain the bottom coating liquid; then coat the bottom coating liquid onto the surface of the high-strength structural steel substrate and pre-cur it at 80℃ for 20min to obtain a dry film with a thickness of 10μm, thus obtaining the interfacial corrosion inhibitor layer structural steel substrate.

[0125] Step 4: Preparation of high-strength, corrosion-resistant structural steel materials

[0126] Weigh 0.3g of the molybdenum-modified barrier filler prepared in Example 6 and 100.0mL of hybrid film-forming liquid and add them to the reaction vessel and stir evenly to obtain a surface coating liquid; then coat the surface coating liquid onto the surface of the interfacial corrosion inhibitor layer structural steel substrate and cure it at 120℃ for 60min, and then place it at room temperature for 24h to obtain a dry film with a thickness of 21μm, thus obtaining a high-strength corrosion-resistant structural steel material.

[0127] Comparative Example 1

[0128] The difference between this comparative example and Example 9 is that step II is omitted in the preparation process of the cerium-modified corrosion inhibitor used in step three.

[0129] Comparative Example 2

[0130] The difference between this comparative example and Example 9 is that step ② is omitted in the preparation process of the molybdenum-modified barrier filler used in step four.

[0131] Comparative Example 3

[0132] The difference between this comparative example and Example 9 is that step three is omitted, and in step four, the high-strength structural steel substrate prepared in step two is used to replace the interfacial corrosion inhibitor layer structural steel substrate.

[0133] Performance testing:

[0134] The yield strength and tensile strength of the high-strength corrosion-resistant structural steel materials prepared in Examples 7-9 and Comparative Examples 1-3 were tested in accordance with the standard GB / T 228.1-2021 "Metallic materials - Tensile testing - Part 1: Test method at room temperature".

[0135] The Charpy impact absorption energy of the high-strength, corrosion-resistant structural steel materials prepared in Examples 7-9 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 229-2020 "Metallic Materials Charpy Pendulum Impact Test Method".

[0136] The neutral salt spray corrosion resistance time of the high-strength corrosion-resistant structural steel materials prepared in Examples 7-9 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 10125-2021 "Artificial Atmosphere Corrosion Test - Salt Spray Test".

[0137] The adhesion of the high-strength corrosion-resistant structural steel materials prepared in Examples 7-9 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 31586.1-2015 "Evaluation and acceptance criteria for the adhesion / cohesion (breaking strength) of protective coating systems to steel structures - Part 1: Pull-off test".

[0138] See Table 1 for specific data;

[0139] Table 1 - Performance Test Data for Each Sample

[0140] Project Group Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Yield strength / MPa 692 694 695 688 690 685 Tensile strength / MPa 781 782 782 775 777 771 Charpy shock absorption energy / J 64 65 65 59 61 57 Neutral salt spray corrosion resistance time / h 840 840 840 610 680 520 Adhesion / MPa 9.1 9.2 9.3 7.5 8.1 6.9

[0141] Data Analysis:

[0142] A comparative analysis of the data in Table 1 reveals that the high-strength, corrosion-resistant structural steel material prepared by this invention exhibits a yield strength of 695 MPa, a tensile strength of 782 MPa, a Charpy impact absorption energy of 65 J, a neutral salt spray corrosion resistance time of 840 h, and an adhesion strength of 9.3 MPa. All these data are superior to those of the comparative example, indicating that…

[0143] In Comparative Example 1, the interface layer structure regulated by cerium was not formed on the side near the steel substrate, resulting in a relatively simple transition relationship between the underlying functional phase and the hybrid film-forming liquid. The interface region had insufficient ability to mitigate disturbances in the service environment. As the external medium gradually migrated inward along the surface defects or microchannels, the region near the steel substrate was more prone to local state fluctuations, which weakened the originally continuous adhesion relationship between the coating and the substrate. This change not only weakened the support of the underlying region for the overlying surface layer, but also further amplified the coupling effect between local stress and local corrosion, making it difficult to maintain synchronous coordination between the load transfer process and the interface evolution process. Ultimately, the sample was more prone to early interface instability and the resulting overall state decay under long-term service conditions.

[0144] In Comparative Example 2, the outer layer system did not form a composite barrier structure after molybdenum participation, resulting in insufficient continuity and densification of the surface layer. The migration process of the external medium from the surface to the interior was more likely to unfold along a relatively direct path. Since the surface layer failed to effectively bear the front-end blocking effect, the bottom layer was exposed to the continuous disturbance of moisture, oxygen and corrosive ions earlier. The original stepwise action sequence along the thickness direction was compressed, and the environmental load borne by the interface layer increased accordingly. At the same time, the weakening of the surface structure integrity also affected the stability of the hybrid network under the combined action of environment and load, making local loose areas more likely to evolve into the starting point of subsequent penetration and instability. As a result, the interlayer coordination relationship of the sample tended to weaken during service, and the system as a whole showed more obvious early fluctuation characteristics.

[0145] In Comparative Example 3, after the original layered configuration consisting of an interface corrosion inhibitor layer and an outer barrier layer was replaced by a single-layer hybrid structure, the two types of functional phases lost their spatial basis for acting on specific areas along the thickness direction. This caused the boundaries of the interaction of each component in the same curing system to become blurred. Since a relatively clear interface transition region could not be formed on the side closer to the steel substrate, and the continuous structure dominated by the integrity of the outer layer could not be maintained on the side farther from the steel substrate, local superposition of medium migration, interface evolution and stress transfer within the layer was more likely to occur. Although this single-layer juxtaposition method retained the functional components themselves, it was difficult to establish a structural relationship of gradual lag from the outside to the inside and gradual stability from the inside to the outside. This resulted in a lack of sharing and compensation between adjacent layers in local weak parts, which ultimately made the sample more prone to insufficient overall coordination under long-term environmental action and external load conditions.

[0146] In conclusion, the technical concept of this application is not reflected in the independent introduction of a single filler or a single step, but rather in establishing a composite system with a division of labor along the thickness direction around the steel substrate-interface region-surface region. The cerium-modified corrosion inhibitor filler is positioned close to the steel substrate, providing a clear transition foundation for the interface region. The molybdenum-modified barrier filler is arranged on the outer layer, linking the transmission path of the external medium with the surface structure. The hybrid film-forming liquid further serves as a continuous phase, connecting the two types of functional components within the same curing network. Compared to simply changing a single component, retaining only partial modification, or changing the layered structure to a single-layer mixture, the interface evolution, medium migration, and intralayer stress transmission in this system do not occur in isolation. Instead, they exhibit a sequential and mutually restrictive operational characteristic along the thickness direction, thus forming an overall structural relationship different from conventional parallel addition methods.

[0147] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0148] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," 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. In this specification, illustrative expressions of the above terms do not necessarily refer 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.

[0149] 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 specific implementations. 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. A method for preparing a high-strength, corrosion-resistant structural steel material, characterized in that, Includes the following steps: S1. The composite steel substrate is added to the melting furnace and heated and melted under nitrogen. After the melt is uniform, it is poured into the mold to form a steel billet. After natural cooling and demolding, a high-strength structural steel substrate is obtained. S2. Cerium-modified corrosion inhibitor filler and hybrid film-forming liquid are added to the reaction vessel and stirred until evenly dispersed to obtain the bottom coating liquid. The bottom coating liquid is then coated on the surface of the high-strength structural steel substrate, and post-treatment is performed to obtain the interfacial corrosion inhibitor layer structural steel substrate. S3. Molybdenum-modified barrier filler and hybrid film-forming liquid are added to the reaction vessel and stirred until evenly dispersed to obtain a surface coating liquid. The surface coating liquid is then coated on the surface of the interfacial corrosion inhibitor structural steel substrate, and post-treatment is performed to obtain high-strength corrosion-resistant structural steel material.

2. The method for preparing a high-strength, corrosion-resistant structural steel material according to claim 1, characterized in that, In step S1, the composite steel substrate is obtained by mixing iron, graphite, manganese, silicon, chromium, nickel, copper, molybdenum, niobium and titanium in a ratio of 1900-1920g:1-2g:24-32g:5-6g:10-12g:8-10g:6-8g:3-5g:1g:1g; in step S2, the ratio of cerium-modified corrosion inhibitor to hybrid film-forming solution is 2-3g:100mL, wherein the dry film thickness of the bottom coating solution is 8-12μm; in step S3, the ratio of molybdenum-modified barrier filler to hybrid film-forming solution is 0.2-0.4g:100mL, wherein the dry film thickness of the surface coating solution is 18-24μm.

3. The method for preparing a high-strength, corrosion-resistant structural steel material according to claim 1, characterized in that, The cerium-modified corrosion inhibitor filler was prepared by the following method: A1. Add the tungstate mixture to the reactor, then add the metal salt mixture dropwise while controlling the reactor temperature at 60-70℃ and the pH of the reaction system at 9.5-10.

2. After the addition is complete, continue to keep the mixture warm and stir for 6-8 hours. The zinc aluminum tungstate precursor is then obtained through post-processing. A2. Add zinc aluminum tungstate precursor and deionized water to the reactor and stir until uniform. Then add cerium nitrate hexahydrate and stir until uniform. Next, add 30 wt% hydrogen peroxide solution and adjust the pH of the reaction system to 8.3-8.8 with 25-28 wt% ammonia. Then heat the reactor to 35-45℃ and keep it at that temperature for 2-4 hours. The post-treatment yields cerium-modified corrosion inhibitor filler.

4. The method for preparing a high-strength, corrosion-resistant structural steel material according to claim 3, characterized in that, In step A1, the metal salt mixture is obtained by mixing zinc nitrate hexahydrate, aluminum nitrate nonahydrate, and deionized water in a ratio of 16-18g:5-8g:120mL; the tungstate mixture is obtained by mixing sodium tungstate dihydrate, sodium hydroxide, and deionized water in a ratio of 7-9g:8-10g:160mL.

5. The method for preparing a high-strength, corrosion-resistant structural steel material according to claim 3, characterized in that, In step A1, the metal salt mixture and the tungstate mixture are mixed at a volume ratio of 5 mL: 6-7 mL, and the addition time is 2-3 h. In step A2, the ratio of the zinc aluminum tungstate precursor, deionized water, cerium nitrate hexahydrate and 30 wt% hydrogen peroxide solution is 21-27 g: 500 mL: 9-12 g: 1-2 mL.

6. The method for preparing a high-strength, corrosion-resistant structural steel material according to claim 1, characterized in that, The molybdenum-modified barrier filler was prepared by the following method: B1. Add graphene oxide and 1.5wt% hydrochloric acid aqueous solution to the reaction vessel and stir until evenly dispersed. Then add aniline and m-aminobenzenesulfonic acid. Subsequently, cool the reaction vessel to 0-5℃ and add 10wt% ammonium persulfate aqueous solution dropwise. After the addition is completed, continue to keep it at 0-5℃ and stir for 5-7 hours. The post-processing yields polyaniline graphene precursor. B2. Add polyaniline graphene precursor, anhydrous ethanol and deionized water to the reaction vessel and stir until uniformly mixed. Then add ammonium heptamolybdate tetrahydrate and glacial acetic acid to adjust the pH of the reaction system to 4.0-4.

5. Then heat the reaction vessel to 35-45℃ and keep it at that temperature for 2-3 hours. The post-treatment yields molybdenum modified barrier filler.

7. The method for preparing a high-strength, corrosion-resistant structural steel material according to claim 6, characterized in that, In step B1, the ratio of graphene oxide, 1.5 wt% hydrochloric acid aqueous solution, aniline, m-aminobenzenesulfonic acid and 10 wt% ammonium persulfate aqueous solution is 2-3 g: 500 mL: 2-3 g: 4-5 g: 40-60 mL; in step B2, the ratio of polyaniline graphene precursor, anhydrous ethanol, deionized water and ammonium heptamolybdate tetrahydrate is 9-10 g: 100 mL: 100 mL: 3-4 g.

8. The method for preparing a high-strength, corrosion-resistant structural steel material according to claim 1, characterized in that, The preparation method of the hybrid film-forming solution is as follows: anhydrous ethanol, deionized water and glacial acetic acid are added to a reaction vessel and stirred evenly. Then, 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane and tetraethyl orthosilicate are added in sequence and stirred. Then, bisphenol A type epoxy resin is added and stirred and dispersed for 30-50 minutes. After standing and degassing, the hybrid film-forming solution is obtained.

9. The method for preparing a high-strength, corrosion-resistant structural steel material according to claim 8, characterized in that, In the preparation of the hybrid film-forming solution, the ratio of anhydrous ethanol, deionized water, glacial acetic acid, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, tetraethyl orthosilicate, and bisphenol A epoxy resin is 40 mL:10 mL:1 mL:4-6 mL:2-3 mL:4-5 mL:50 g. The hybrid film-forming solution should be used within 4-6 hours.

10. A high-strength, corrosion-resistant structural steel material, characterized in that, The high-strength, rust-resistant structural steel material is prepared using a method for preparing high-strength, rust-resistant structural steel material as described in any one of claims 1-9.

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