Low-hydration-heat type intelligent slow-release corrosion-resistant cementitious system for ocean engineering

Abstract

The invention discloses a low-hydration-heat intelligent slow-release corrosion-resistant cementitious material for ocean engineering, and relates to the technical field of cementitious materials for ocean engineering. The gelling system is composed of 30%-60% of high-silicon high-iron sulphoaluminate cement clinker, 2%-15% of a setting time and activity regulator, 30%-60% of a mineral active admixture and 1%-3% of an intelligent slow-release anticorrosive agent. The clinker is prepared by calcining at 1250-1350 DEG C, and the intelligent slow-release anticorrosive agent is an inclusion supramolecular material of beta-cyclodextrin and benzotriazole (the molar ratio is 1: 1-1: 1.5). Through cooperation of mineral composition optimization, microstructure densification and intelligent protection, low hydration heat, high compactness and targeted corrosion prevention are achieved, temperature cracks are effectively reduced, marine environment erosion is resisted, and the service life of an engineering structure is prolonged.

Description

Technical Field

[0001] This invention relates to the field of cementitious materials for marine engineering, and more specifically to a low-heat hydration intelligent slow-release corrosion-resistant cementitious system for marine engineering. Background Technology

[0002] With the continuous and in-depth development and research of deep-sea engineering in my country, large-volume concrete structures in marine engineering (such as bridge piers for cross-sea bridges, offshore wind power foundations, and deep-water wharf pile foundations) face the dual challenges of concentrated heat release from hydration and the highly corrosive marine environment. During the hardening process of large-volume concrete, the hydration reaction of the cementitious materials releases a large amount of heat, with the core temperature reaching 60-80℃, while the surface dissipates heat rapidly, forming a huge internal and external temperature difference (reaching 20-40℃), generating thermal stress and leading to early cracking. These cracks provide rapid pathways for corrosive media such as chloride ions and sulfates, accelerating structural deterioration and seriously affecting the service life and safety performance of marine engineering structures. The marine environment poses an extremely severe challenge to concrete structures, with durability issues being particularly prominent. The corrosion of concrete structures by the marine environment is mainly manifested in the coupled effects of multiple deterioration mechanisms such as chloride ion corrosion, sulfate corrosion, carbonation, and freeze-thaw cycles.

[0003] Traditional silicate cement-based cementitious materials generate a large amount of heat during hydration, producing a significant amount of easily corroded calcium hydroxide. Furthermore, their porous internal structure provides pathways for corrosive media to penetrate. Under the combined effects of marine environmental factors such as wet-dry cycles, freeze-thaw cycles, and wave erosion, the deterioration process of concrete is drastically accelerated. Seawater contains chloride ions at concentrations as high as 19 g / L. Chloride ions penetrate the concrete, damaging the passivation film on the steel reinforcement, leading to steel corrosion. The corrosion products expand 3-6 times in volume, causing concrete cracking and spalling. Sulfate ions in seawater react with cement hydration products to form ettringite and gypsum, which expand in volume, causing concrete cracking. These multiple ion reactions collectively lead to structural performance degradation and a significant reduction in service life. In cold sea areas, freeze-thaw cycles cause repeated freezing and thawing of water in the concrete pores, generating expansion stress and causing surface spalling. These factors make improving the physical density and chemical stability of cementitious materials a key research focus.

[0004] In terms of corrosion resistance, traditional cementitious material systems exhibit inherent limitations when facing the complex chemical corrosion of the marine environment. High concentrations of chlorides, magnesium sulfate, and other substances not only induce physical crystallization stress but also undergo a series of complex chemical transformations with cement hydration products, such as generating expansive ettringite and gypsum, and promoting the decalcification and decomposition of the CSH gel, the main strength component, ultimately transforming into MSH, which has no cementing capacity. This chemical corrosion leads to softening and spalling of the concrete surface, complete loss of strength, and corrosion of the reinforcing steel, resulting in reduced structural strength. Currently, although performance can be improved to some extent by using large amounts of mineral admixtures, how to fundamentally design a new cementitious system that can coexist with the marine corrosive environment for a long time and possesses both high chemical stability and low environmental impact remains a major challenge for current research and engineering practice.

[0005] Sulfoaluminate cement is increasingly used in marine engineering due to its excellent resistance to sulfate attack. Among its applications, given its mineral composition, researching its durability and corrosion inhibition measures in seawater environments is crucial for improving engineering safety and extending structural service life. Effectively reducing early-stage temperature cracking in concrete, increasing concrete density, preventing corrosion, ensuring structural stability, and delaying concrete deterioration have become important topics of concern in materials science and engineering.

[0006] Patent WO2019152736A1, entitled "Geopolymer Composition for Marine Concrete and Preparation Method Thereof," discloses a marine cementitious system using industrial waste such as slag and fly ash as raw materials. Under strong alkali activation, it forms a cementitious body primarily composed of a three-dimensional network structure of aluminosilicates. This system contains almost no calcium hydroxide, fundamentally avoiding chemical corrosion and expansion damage from chloride ions and sulfates. However, its drawbacks are also significant: 1. Stringent construction process: It is sensitive to the concentration, modulus, and curing conditions (usually requiring heat curing) of the alkali activator, making large-scale on-site construction difficult. 2. Long-term performance data is still under development: As a relatively new material, its decades-long durability data in marine environments is still being accumulated. 3. Significant shrinkage: It is prone to high drying shrinkage, posing a risk of cracking. 4. Raw material stability is particularly important: Fluctuations in the composition of raw materials such as fly ash can affect the uniformity of the finished product quality.

[0007] US Patent 20180072433A1, entitled "Cement composition for marine structure and method for constructing marine structure using the same," discloses a conventional cement system characterized by the composite use of ultrafine admixtures such as ultrafine fly ash, silica fume, and nano-silica. These particles can physically fill the voids between cement particles, while simultaneously undergoing a pozzolanic reaction that consumes calcium hydroxide, generating more CSH gel and transforming the pore structure from harmful macropores to harmless micropores. Disadvantages include: 1. High requirements for raw material quality: The quality and stability of the ultrafine admixtures are crucial. 2. High viscosity of fresh concrete: High-efficiency water-reducing agents are required, and workability loss may be rapid, necessitating sophisticated construction techniques. 3. Increased costs: The use of ultrafine admixtures and nanomaterials increases material costs.

[0008] Because key marine engineering projects are of great national importance, the requirements for low heat of hydration, high durability, and resistance to salt and corrosion are becoming increasingly important. To improve the workability of cementitious materials and the durability of concrete in marine engineering projects, different cement systems are currently used to achieve these effects, but these are still not the optimal choice for cementitious materials. Summary of the Invention

[0009] In order to overcome the defects and deficiencies in the existing technology, the present invention provides a low-heat hydration intelligent slow-release corrosion-resistant cementing system for marine engineering. The purpose of the present invention is to solve the problems of high early hydration heat release, non-dense cement stone structure, and small amount of seawater entering the cement stone through the voids in the cement stone structure during the hydration reaction process and reacting with the steel reinforcement, thus corroding the steel reinforcement.

[0010] To address the problems existing in the prior art, the present invention is achieved through the following technical solution.

[0011] This invention provides a low-heat hydration type intelligent slow-release corrosion-resistant cementitious system for marine engineering, characterized in that: the cementitious system is composed of high-silica and high-iron sulfoaluminate cement clinker for marine engineering, setting time and activity regulator, mineral active admixtures and intelligent slow-release corrosion inhibitor; By mass percentage, the amount of the high-silica, high-iron sulfoaluminate cement clinker is 30%-60% of the entire cementitious system; the amount of the setting time and activity regulator is 2%-15% of the entire cementitious system; the amount of the mineral active admixture is 30%-60% of the entire cementitious system; and the amount of the intelligent slow-release corrosion inhibitor is 1%-3% of the entire cementitious system. The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then calcining them at a high temperature of 1250℃-1350℃ before grinding. The high-silica, high-iron sulfoaluminate cement raw meal comprises the following components by weight: 40-60 parts calcium-rich material; 2-15 parts of siliceous material; 4-20 parts aluminum material; 0-10 parts of iron material; 10-25 parts of plaster materials; The alkalinity coefficient of the high-silicon, high-iron sulfoaluminate cement raw meal is controlled at 0.95-1.15, and the aluminum-sulfur ratio is controlled at 2.5-3.82. The high-silicon and high-iron sulfoaluminate cement raw meal is calcined to form a mineral composition including calcium sulfoaluminate, dicalcium silicate, calcium ferroaluminate, free gypsum and calcium sulfosilicate, thus obtaining the high-silicon and high-iron sulfoaluminate cement clinker. The intelligent slow-release corrosion inhibitor is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1 to 1:1.5.

[0012] More preferably, the intelligent slow-release corrosion inhibitor is obtained by mixing β-cyclodextrin and benzotriazole in a set ratio, adding a reaction aid, and then grinding the resulting mixture in a planetary ball mill. The ground product is then reacted under low-temperature vacuum drying conditions, and the inclusion complex is obtained after the constant reaction is complete.

[0013] More preferably, the reaction aid is any one of acetone, ethanol, and water.

[0014] More preferably, the mass ratio of the mixture formed by mixing the reaction aid with β-cyclodextrin and benzotriazole is 5:100-10:100.

[0015] More preferably, the low-temperature vacuum drying conditions refer to a temperature of 40℃-60℃ and a vacuum degree of 5pa-50pa.

[0016] More preferably, the calcareous material is any one or a mixture of any proportion of conventional limestone, high-silicon limestone, and high-silicon, high-calcium industrial waste residue; the calcareous material contains ≥44.00% CaO and ≤15.00% SiO2.

[0017] More preferably, the siliceous material is any one or a combination of sandstone, shale and fluorite washing waste in any proportion, wherein the SiO2 content in the siliceous material is ≥70.00%.

[0018] More preferably, the ferrous material is non-ferrous metal ash, magnetite, sulfuric acid slag, or copper slag, and the Fe2O3 content in the ferrous material is ≥30.00%; the aluminum material is bauxite, aluminum ash, or high-iron bauxite, wherein the Al2O3 content in bauxite is ≥50.00%, and the SiO2 content is ≤20%; the Al2O3 content in aluminum ash is ≥65.00%; and the Al2O3 content in high-iron bauxite is ≥50.00%, and the Fe2O3 content is ≥15.00%.

[0019] More preferably, the gypsum material is dihydrate gypsum, anhydrite, mixed gypsum, desulfurized gypsum, phosphogypsum, or fluorogypsum, wherein the SO3 content is ≥25%.

[0020] More preferably, the specific surface area of ​​the high-silica, high-iron aluminate cement clinker is controlled at 320 m². 2 / kg-380m 2 / kg.

[0021] More preferably, the setting time and activity regulator is calcined gypsum, dihydrate gypsum, anhydrite, or a mixed gypsum, with an SO3 content ≥30%.

[0022] More preferably, the active admixture is any two or more of fly ash, slag, pozzolanic materials, metakaolin and limestone mixed in any proportion.

[0023] More preferably, the specific surface area of ​​the active admixture is controlled at 400 m². 2 / kg-450m 2 / kg.

[0024] This invention realizes the application of sulfoaluminate cementitious materials in large-volume concrete from three dimensions: reducing chemical erosion weaknesses through mineral composition optimization, constructing a dense microstructure through highly active admixtures and a low water-cement ratio, and providing surface protection for the steel reinforcement structure through intelligent slow-release corrosion inhibitors, thereby providing multiple protections for the entire concrete system, ultimately forming a synergistic corrosion-resistant system of physical barrier + chemical stability + electrochemical protection.

[0025] Firstly, considering the design direction of the main minerals, calcium sulfoaluminate minerals, dicalcium silicate minerals, and aluminoferrite minerals are used to achieve the characteristics of high early strength, good durability, and strong resistance to seawater erosion in the main cementitious material. According to the application scenario, the mineral composition in the clinker is designed by reducing the content of calcium sulfoaluminate, increasing the content of dicalcium silicate, increasing the content of iron phase, and controlling the content of free gypsum. This achieves the early strength support formed by the alternation of high-sulfur ettringite and low-sulfur ettringite. CSH gel has strong adhesion and presents fibrous, network, and can encapsulate and cement the crystalline phases such as AFm and ettringite. Amorphous aluminum glue and iron glue fill the gaps formed by ettringite and other products, resulting in uniform strength development of cement stone. The continuous hydration of gel fills the gaps and improves the density of cement stone, forming an ordered and dense structure of "crystalline phase skeleton + gel phase filling". These hydration products work together to construct the basic structure of cement stone, helping to improve the integrity and strength of the system. Secondly, a multi-mineral synergistic design constructs a composite structure of "high-iron, high-silica calcium sulfoaluminate clinker system + active admixtures + intelligent slow-release corrosion inhibitors": mineral admixtures reduce the concentration of various ions in the system, alleviate the heat release during hydration of the ferroaluminate cement system, and allow early free gypsum to slowly dissolve and react with anhydrous calcium sulfoaluminate to generate low-sulfur ettringite, thereby reducing the early heat release rate and gradually increasing the strength of the cement stone. The reduction of Ca(OH)2 concentration and the organic retarder effectively slow down the early heat release rate and reduce temperature cracks. The active admixtures optimize the gel structure, and the multi-component synergy achieves a comprehensive performance breakthrough of "low heat release, high corrosion resistance, high strength, and low shrinkage".

[0026] Furthermore, in this system, the intelligent slow-release corrosion inhibitor is prepared by mechanical force that micronizes the solid particles and brings them into close contact. With the help of trace solvent molecules, the benzene rings of benzotriazole molecules diffuse into the CD cavity, thereby forming a supramolecular system in which the supramolecular host β-cyclodextrin encapsulates and loads the organic compound benzotriazole (BTA), which has the functions of slowing coagulation and preventing steel corrosion.

[0027] The core of this intelligent release system is a "pH-regulated molecular hydrophilicity / hydrophobicity switch".

[0028] 1) Dormant phase (normal high pH environment, such as concrete pore fluid pH>12.5): At this point, the corrosion inhibitor molecule—benzotriazole-based material—is in a stable state. Its hydrophobic benzene ring moiety is successfully encapsulated within the hydrophobic cavity of the cyclodextrin, forming a stable inclusion complex.

[0029] The corrosion inhibitor is "locked" in the cyclodextrin and fixed in the cement matrix, so it will not be lost ineffectively or have unnecessary side reactions with other cement components.

[0030] 2) Activation and release phase (carbonization of corrosion-retarding concrete occurs, pH decreases locally): When concrete carbonization or chloride ion infiltration causes steel reinforcement to begin to corrode, the microenvironment on the steel reinforcement surface becomes acidic (pH can drop below 9). Under acidic conditions, the nitrogen atom in BTA molecules combines with a hydrogen ion and a calcium ion, becoming a positively charged cation.

[0031] This protonation process greatly enhances the hydrophilicity of the molecules. The hydrophobic molecules, which were originally tightly bound to the hydrophobic cavity of the cyclodextrin, become hydrophilic ions. According to the principle of "like dissolves like," the hydrophobic environment exerts a strong repulsive force on the bound molecules. The inclusion effect between the corrosion inhibitor molecules and the cyclodextrin is disrupted, causing the BTA to detach from the cyclodextrin cavity. The corrosion inhibitor is then intelligently released near the steel reinforcement, encapsulating areas prone to corrosion.

[0032] 3) The stage where it takes effect: The released corrosion inhibitor molecules are quickly adsorbed on the active anodic region of the steel bar surface, forming a monomolecular protective film that effectively prevents the continued dissolution of iron ions, thereby inhibiting the corrosion process.

[0033] Compared with the prior art, the beneficial technical effects of the present invention are as follows: 1. Constructing a synergistic corrosion-resistant system to achieve a multi-layered protective closed loop: This invention forms a synergistic corrosion-resistant system of "physical barrier + chemical stability + electrochemical protection" from three core dimensions: mineral composition optimization, microstructure densification, and intelligent protection empowerment, comprehensively solving the corrosion problem of cementitious materials in marine environments. By precisely controlling the proportion of minerals such as calcium sulfoaluminate, dicalcium silicate, and calcium aluminoferrite in high-silica and high-iron sulfoaluminate cement clinker, the chemical weaknesses susceptible to corrosion are reduced; with the synergistic effect of highly active admixtures and low water-cement ratio, an ordered and dense structure of "crystalline phase skeleton + gel phase filling" is constructed—fibrous and network-like CSH gel encapsulates and binds crystalline phases such as AFm and ettringite, while amorphous aluminum and iron gels fill the pores, significantly reducing the penetration channels of corrosive media; intelligent slow-release corrosion inhibitors provide targeted electrochemical protection for steel bars. The three form a protective closed loop, which is significantly superior to traditional cementitious systems with a single protection mechanism.

[0034] 2. Outstanding Low Heat of Hydration Characteristics, Solving the Problem of Temperature Cracks: Addressing the issue of temperature difference cracks caused by concentrated heat of hydration in large-volume concrete, this invention achieves low heat release regulation through multi-component synergistic design. On one hand, it optimizes the clinker mineral composition, reducing the content of calcium sulfoaluminate and increasing the content of dicalcium silicate and iron phase, thus reducing the early-stage heat release peak. On the other hand, the introduction of mineral admixtures reduces the ion concentration of the system, allowing early-stage free gypsum to slowly dissolve and react with anhydrous calcium sulfoaluminate to generate low-sulfur ettringite, slowing down the heat release rate. Simultaneously, it reduces the Ca(OH)2 concentration and further mitigates early-stage heat release through organic retarding. Actual measured data show that the cementitious system of this invention has a minimum 1-day heat of hydration of only 182.6 J / g and a maximum 28-day heat of hydration of 270.1 J / g, far lower than the traditional aluminoferrite cement system (comparative example, 302.5 J / g hydration heat at 128 days). This effectively controls the internal and external temperature differences within a safe range, reduces the occurrence of temperature cracks, and solves the industry pain point of high early-stage heat release in traditional sulfoaluminate cement.

[0035] 3. Stable and balanced strength development with excellent long-term performance: The cementitious system of this invention achieves a balanced development characteristic of early-stage strength support and continuous strength growth in later stages. The 1-day compressive strength is ≥32.5 MPa, meeting the early construction load-bearing requirements; the 28-day compressive strength reaches a maximum of 58.6 MPa, significantly higher than the standard requirement of 42.5 MPa, and superior to traditional cement systems (comparative example: 128-day compressive strength 52.9 MPa). The stability of strength growth stems from the synergistic hydration of mineral components: the mineral composition of high-silica and high-iron clinker ensures a solid foundation for early strength, while the active admixtures continuously undergo pozzolanic reactions during hydration, generating more CSH gel, continuously filling pores and creating a dense structure, achieving long-term strength improvement. Simultaneously, the 28-day free expansion rate of the system is controlled at 0.02%-0.05%, meeting standard requirements and eliminating the risk of shrinkage, avoiding structural cracking due to volume deformation and ensuring the long-term stability of the project.

[0036] 4. Intelligent Targeted Corrosion Prevention, Extending Structural Service Life: The intelligent slow-release corrosion inhibitor of this invention adopts an inclusion supramolecular system of β-cyclodextrin and benzotriazole (BTA), possessing intelligent characteristics of "pH response-targeted release-precise protection". In the normal high pH environment of concrete (pore fluid pH>12.5), the hydrophobic benzene ring of BTA is encapsulated by the hydrophobic cavity of cyclodextrin, forming a stable inclusion complex, avoiding ineffective loss and side reactions; when concrete carbonization or chloride ion intrusion leads to acidification of the microenvironment on the surface of steel reinforcement (pH≤9), the BTA molecule is protonated and transformed into a hydrophilic cation, which is destroyed by the inclusion effect of cyclodextrin, and is released to the corrosion site in a targeted manner, rapidly adsorbing to form a monomolecular protective film, preventing the dissolution of iron ions. This mechanism significantly improves the utilization rate of corrosion inhibitors. Compared with the system without the addition of intelligent slow-release corrosion inhibitors (comparative example, corrosion resistance coefficient of 1.02 at 328 days), the corrosion resistance coefficient of this invention reaches up to 1.19 at 28 days, which significantly enhances the resistance to marine corrosive media such as chloride ions and sulfates, effectively delays steel corrosion and concrete deterioration, and greatly extends the service life of marine engineering structures.

[0037] 5. Strong raw material adaptability and significant advantages in construction and economy: This invention is compatible with industrial waste residues (such as aluminum ash residue, sulfuric acid residue, desulfurization gypsum, slag, etc.) in terms of raw material selection. Calcareous materials can be selected from conventional limestone, high-silica limestone and high-silica and high-calcium industrial waste residues. Siliceous materials can be selected from industrial by-products such as fluorite washing waste residues, which not only reduces raw material costs, but also realizes the resource utilization of solid waste, which is in line with the development trend of green building materials. In terms of construction performance, the system controls particle size distribution (D10≤2.0μm, D90≤40μm) through mixing with a V-type mixer, resulting in good workability of fresh concrete. No special curing conditions are required. Compared with the alkali-activated system of patent WO2019152736A1 (which requires heat curing and has a demanding construction process), it is more suitable for large-scale on-site construction. Compared with the ultrafine admixture system of patent US20180072433A1 (which requires a high-efficiency water-reducing agent and is costly), this invention does not rely on nanomaterials or expensive ultrafine admixtures, thus controlling production costs while ensuring performance and possessing stronger engineering application feasibility.

[0038] 6. Comprehensive corrosion resistance, adaptable to complex marine environments: Addressing the multiple coupled degradation mechanisms of chloride ion corrosion, sulfate corrosion, carbonization, and freeze-thaw cycles in marine environments, this invention achieves comprehensive corrosion resistance enhancement. The system's dense microstructure reduces the intrusion of corrosive media, and the high-silicon, high-iron clinker mineral composition prevents CSH gel decalcification and inhibits excessive expansion of ettringite and gypsum. The intelligent slow-release corrosion inhibitor specifically addresses steel reinforcement corrosion, achieving a 28-day corrosion resistance coefficient ≥1.10, with a maximum of 1.19, superior to systems without added admixtures (Comparative Example 2, corrosion resistance coefficient 1.05) and without added corrosion inhibitors (Comparative Example 3, corrosion resistance coefficient 1.02). This characteristic enables the cementitious system of this invention to adapt to different marine environments (including freeze-thaw cycle scenarios in cold sea areas), effectively resisting the synergistic damage of multiple corrosive factors and solving the major problem of insufficient durability of traditional cementitious materials in complex marine corrosive environments. Attached Figure Description

[0039] Figure 1 This is a scanning electron microscope image of the hydration products of the gelation system in Example 1 of the present invention; Figure 2 The lithofacies of high-silica and high-iron sulfoaluminate cement clinker in Example 1 of this invention Figure 1 .

[0040] Figure 3 The lithofacies of high-silica and high-iron sulfoaluminate cement clinker in Example 1 of this invention Figure 2 . Detailed Implementation

[0041] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0042] Example 1 As a preferred embodiment of the present invention, this embodiment provides a low-heat intelligent slow-release corrosion-resistant cementitious system for marine engineering. By mass percentage, the cementitious system consists of high-silica, high-iron sulfoaluminate cement clinker, accounting for 51% of the total cementitious system; a setting time and activity regulator, accounting for 5% of the total cementitious system; mineral active admixtures, accounting for 43% of the total cementitious system; and an intelligent slow-release corrosion inhibitor, accounting for 1% of the total cementitious system.

[0043] Among them, refer to the appendix of the instruction manual Figure 1 Appendix Figure 2 and attached Figure 3As shown, the high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then grinding them after calcination at 1280℃.

[0044] High-silica, high-iron sulfoaluminate cement raw meal, by weight, includes: 45 parts limestone (CaO 54% and SiO2 0.62%) 10 parts of sandstone (SiO2=70.25%); 15 parts of aluminum slag ash (Al2O3=68.23%, SiO2=2.12%). 10 portions of sulfuric acid residue (F2O3=45.31%). 20 parts of fluorinated gypsum (SO3=31.25%); The basicity coefficient of the raw meal is 0.95, and the aluminum-sulfur ratio is controlled at 3.82. The main mineral composition of the high-silicon, high-iron sulfoaluminate cement raw meal after calcination is calcium sulfoaluminate, dicalcium silicate, calcium aluminoferrite, free gypsum, and calcium sulfosilicate. The specific surface area of ​​the high-silicon, high-iron sulfoaluminate cement clinker is controlled at 350 m². 2 / kg.

[0045] In this embodiment, the setting time and activity regulator used is calcined gypsum with an SO3 content of 31.20%. The mineral active admixtures are slag and limestone, and the specific surface area of ​​the mineral active admixtures is controlled at 400 m². 2 / kg.

[0046] The intelligent slow-release corrosion inhibitor used in this embodiment is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1; specifically, the intelligent slow-release corrosion inhibitor is prepared by mixing β-cyclodextrin and benzotriazole in a molar ratio of 1:1, adding 5% acetone as a reaction aid as a mass fraction of the mixture of β-cyclodextrin and benzotriazole, and grinding the mixture of acetone, β-cyclodextrin and benzotriazole in a planetary ball mill for 30 minutes. The resulting paste or powder is dried at 40°C and 50 Pa vacuum for 10 hours to ensure complete reaction, thus obtaining the inclusion complex.

[0047] Example 2 As another preferred embodiment of the present invention, this embodiment provides a low-heat hydration type intelligent slow-release corrosion-resistant cementitious system for marine engineering. By mass percentage, the cementitious system consists of high-silica, high-iron sulfoaluminate cement clinker, accounting for 30% of the total cementitious system; setting time and activity regulator, accounting for 8.6% of the total cementitious system; mineral active admixture, accounting for 60% of the total cementitious system; and intelligent slow-release corrosion inhibitor, accounting for 1.4% of the total cementitious system.

[0048] The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then grinding them after calcination at 1250℃.

[0049] High-silica, high-iron sulfoaluminate cement raw meal, by weight, includes: 60 parts limestone (CaO 44.00% and SiO2 15.01%). Two portions of fluorite washing waste residue (SiO2=82.10%) 17 parts of bauxite (Al2O3=68.23%, SiO2=2.12%). Eight portions of copper slag (F2O3=42.15%). The raw meal contains 13 parts phosphogypsum (SO3=42.14%), with an alkalinity coefficient of 1.02 and an aluminum-sulfur ratio controlled at 2.21. The main mineral composition of the calcined high-silicon, high-iron sulfoaluminate cement raw meal is calcium sulfoaluminate, dicalcium silicate, calcium aluminoferrite, free gypsum, and calcium sulfosilicate. The specific surface area of ​​the high-silicon, high-iron sulfoaluminate cement clinker is controlled at 358 m². 2 / kg.

[0050] In this embodiment, the setting time and activity regulator used is anhydrite with an SO3 content of 41.12%. The mineral active admixtures are metakaolin and fly ash, and the specific surface area of ​​the mineral active admixtures is controlled at 450 m². 2 / kg.

[0051] The intelligent slow-release corrosion inhibitor used in this embodiment is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1.5; specifically, the intelligent slow-release corrosion inhibitor is prepared by mixing β-cyclodextrin and benzotriazole at a molar ratio of 1:1.5, adding 10% ethanol by mass of the mixture of β-cyclodextrin and benzotriazole as a reaction aid, and grinding the mixture of ethanol, β-cyclodextrin and benzotriazole in a planetary ball mill for 150 min. The resulting paste is then dried at 60°C and 5 Pa vacuum for 18 h to ensure complete reaction, yielding the inclusion complex.

[0052] Example 3 As another preferred embodiment of the present invention, this embodiment provides a low-heat hydration type intelligent slow-release corrosion-resistant cementitious system for marine engineering. By mass percentage, the cementitious system consists of high-silica, high-iron sulfoaluminate cement clinker, accounting for 60% of the total cementitious system; setting time and activity regulator, accounting for 2% of the total cementitious system; mineral active admixture, accounting for 36.5% of the total cementitious system; and intelligent slow-release corrosion inhibitor, accounting for 1.5% of the total cementitious system.

[0053] The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then grinding them after calcination at 1350℃.

[0054] High-silica, high-iron sulfoaluminate cement raw meal, by weight, includes: 40 parts of white clay (CaO content 51.01% and SiO2 content 16.2%). 13 shale samples (SiO2=71.23%); 20 parts of bauxite (Al2O3=59.12%, SiO2=2.12%). Two parts of magnetite (F2O3=49.47%). The raw meal contains 25 parts anhydrite (SO3=49.56%), with an alkalinity coefficient of 1.15 and an aluminum-sulfur ratio controlled at 2.12. The main mineral composition of the calcined high-silicon, high-ferrous sulfoaluminate cement raw meal is calcium sulfoaluminate, dicalcium silicate, calcium aluminoferrite, free gypsum, and calcium sulfosilicate. The specific surface area of ​​the high-silicon, high-ferrous sulfoaluminate cement clinker is controlled at 326 m². 2 / kg.

[0055] The setting time and activity regulator used in this embodiment is mixed gypsum with an SO3 content of 38.12%. The mineral active admixture is Hainan volcanic ash and slag, and the specific surface area of ​​the mineral active admixture is controlled at 420 m². 2 / kg.

[0056] The intelligent slow-release corrosion inhibitor used in this embodiment is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1.2; specifically, the intelligent slow-release corrosion inhibitor is prepared by mixing β-cyclodextrin and benzotriazole at a molar ratio of 1:1.2, adding 5% water (by mass of the mixture of β-cyclodextrin and benzotriazole) as a reaction aid, and grinding the mixture of water, β-cyclodextrin and benzotriazole in a planetary ball mill for 120 min. The resulting paste is then dried at 50°C and 40 Pa vacuum for 24 h to ensure complete reaction, yielding the inclusion complex.

[0057] Example 4 As another preferred embodiment of the present invention, this embodiment provides a low-heat hydration type intelligent slow-release corrosion-resistant cementitious system for marine engineering. By mass percentage, the cementitious system consists of high-silica, high-iron sulfoaluminate cement clinker, accounting for 47% of the total cementitious system; setting time and activity regulator, accounting for 12% of the total cementitious system; mineral active admixture, accounting for 39% of the total cementitious system; and intelligent slow-release corrosion inhibitor, accounting for 2% of the total cementitious system.

[0058] The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then grinding them after calcination at 1300℃.

[0059] High-silica, high-iron sulfoaluminate cement raw meal, by weight, includes: 57 portions of calcium carbide slag (CaO content 67.02%, SiO2 content 8.20%). 13 parts of sandstone (SiO2=75.55%); 20 parts of iron-aluminate bauxite (Al2O3=53.45%, Fe2O3 content is 22.42%, SiO2=2.12%). The raw meal contains 10 parts of desulfurized gypsum (SO3=45.95%), with an alkalinity coefficient of 1.00 and an aluminum-sulfur ratio controlled at 2.52. The main mineral composition of the calcined high-silicon, high-iron sulfoaluminate cement raw meal is calcium sulfoaluminate, dicalcium silicate, calcium ferroaluminate, free gypsum, and calcium sulfosilicate. The specific surface area of ​​the high-silicon, high-iron sulfoaluminate cement clinker is controlled at 360 m². 2 / kg.

[0060] In this embodiment, the setting time and activity regulator used is mixed gypsum with an SO3 content of 45.95%. The mineral active admixtures are Hainan volcanic ash and limestone, and the specific surface area of ​​the mineral active admixtures is controlled at 400 m². 2 / kg.

[0061] The intelligent slow-release corrosion inhibitor used in this embodiment is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1.3; specifically, the intelligent slow-release corrosion inhibitor is prepared by mixing β-cyclodextrin and benzotriazole at a molar ratio of 1:1.3, adding 8% acetone by mass of the mixture of β-cyclodextrin and benzotriazole as a reaction aid, and grinding the mixture of acetone, β-cyclodextrin and benzotriazole in a planetary ball mill for 100 min. The resulting paste or powder is dried at 42°C and 25 Pa vacuum for 24 h to ensure complete reaction, thus obtaining the inclusion complex.

[0062] Example 5 As a preferred embodiment of the present invention, this embodiment provides a low-heat hydration type intelligent slow-release corrosion-resistant cementitious system for marine engineering. By mass percentage, the cementitious system consists of high-silica, high-iron sulfoaluminate cement clinker, accounting for 40% of the total cementitious system; setting time and activity regulator, accounting for 15% of the total cementitious system; mineral active admixture, accounting for 42% of the total cementitious system; and intelligent slow-release corrosion inhibitor, accounting for 3% of the total cementitious system.

[0063] The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then grinding them after calcination at 1320℃.

[0064] High-silica, high-iron sulfoaluminate cement raw meal, by weight, includes: 55 parts of high-silica limestone (CaO content 48.50% and SiO2 content 12.30%). 15 parts of sandstone (SiO2=78.60%); 4 parts of bauxite (Al2O3=52.10%, SiO2=18.30%). 5 parts of magnetite (Fe2O3=47.80%); 18 parts of desulfurized gypsum (SO3=38.70%); The alkalinity coefficient of the raw meal is 1.05, and the aluminum-sulfur ratio is controlled at 2.5. The main mineral composition of the high-silicon and high-iron sulfoaluminate cement raw meal after calcination is calcium sulfoaluminate, dicalcium silicate, calcium ferroaluminate, free gypsum, and calcium sulfosilicate. The specific surface area of ​​the high-silicon and high-iron sulfoaluminate cement clinker is controlled at 380 m² / kg.

[0065] The setting time and activity regulator used in this embodiment is gypsum dihydrate with an SO3 content of 35.60%. The mineral active admixtures are fly ash and metakaolin, and the specific surface area of ​​the mineral active admixtures is controlled at 430 m² / kg.

[0066] The intelligent slow-release corrosion inhibitor used in this embodiment is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1.1; specifically, the intelligent slow-release corrosion inhibitor is prepared by mixing β-cyclodextrin and benzotriazole in a molar ratio of 1:1.1, adding 7% ethanol by mass of the mixture of β-cyclodextrin and benzotriazole as a reaction aid, and grinding the mixture of ethanol, β-cyclodextrin and benzotriazole in a planetary ball mill for 90 min. The resulting paste is then dried at 48°C and 30 Pa vacuum for 16 h to ensure complete reaction, yielding the inclusion complex.

[0067] Example 6 As a preferred embodiment of the present invention, this embodiment provides a low-heat hydration type intelligent slow-release corrosion-resistant cementitious system for marine engineering. By mass percentage, the cementitious system consists of high-silica, high-iron sulfoaluminate cement clinker, accounting for 45% of the total cementitious system; setting time and activity regulator, accounting for 8% of the total cementitious system; mineral active admixture, accounting for 45% of the total cementitious system; and intelligent slow-release corrosion inhibitor, accounting for 2% of the total cementitious system.

[0068] The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then grinding them after calcination at 1270℃.

[0069] High-silica, high-iron sulfoaluminate cement raw meal, by weight, includes: 48 portions of calcium carbide slag (CaO content 62.30% and SiO2 content 10.50%). 15 samples of shale (SiO2=73.80%). 10 parts of aluminum ash slag (Al2O3=68.50%, SiO2=12.10%). 22 parts of phosphogypsum (SO3=41.30%) The alkalinity coefficient of the raw meal is 1.08, and the aluminum-sulfur ratio is controlled at 3.2. The main mineral composition of the high-silicon and high-iron sulfoaluminate cement raw meal after calcination is calcium sulfoaluminate, dicalcium silicate, calcium aluminoferrite, free gypsum, and calcium sulfosilicate. The specific surface area of ​​the high-silicon and high-iron sulfoaluminate cement clinker is controlled at 320 m² / kg.

[0070] The setting time and activity regulator used in this embodiment is mixed gypsum with an SO3 content of 36.80%. The mineral active admixture is slag and pozzolanic material, and the specific surface area of ​​the mineral active admixture is controlled at 410 m² / kg.

[0071] The intelligent slow-release corrosion inhibitor used in this embodiment is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1.4; specifically, the intelligent slow-release corrosion inhibitor is prepared by mixing β-cyclodextrin and benzotriazole at a molar ratio of 1:1.4, adding 6% water by mass of the mixture as a reaction aid, and grinding the mixture of water, β-cyclodextrin and benzotriazole in a planetary ball mill for 80 min. The ground powder is then dried at 55°C and 15 Pa vacuum for 14 h to ensure complete reaction, resulting in the inclusion complex.

[0072] Example 7 As a preferred embodiment of the present invention, this embodiment provides a low-heat hydration type intelligent slow-release corrosion-resistant cementitious system for marine engineering. By mass percentage, the cementitious system consists of high-silica, high-iron sulfoaluminate cement clinker, accounting for 55% of the total cementitious system; setting time and activity regulator, accounting for 4% of the total cementitious system; mineral active admixture, accounting for 38% of the total cementitious system; and intelligent slow-release corrosion inhibitor, accounting for 3% of the total cementitious system.

[0073] The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then grinding them after calcination at 1330℃.

[0074] High-silica, high-iron sulfoaluminate cement raw meal, by weight, includes: 60 parts limestone (CaO content 53.80% and SiO2 content 8.60%). Eight portions of fluorite beneficiation waste residue (SiO2=71.50%) were collected. Four portions of high-iron bauxite (Al2O3=51.20%, Fe2O3=18.70%, SiO2=16.30%). 10 portions of copper slag (Fe2O3=45.60%). 15 parts of anhydrite (SO3=43.20%); The alkalinity coefficient of the raw meal is 1.12, and the aluminum-sulfur ratio is controlled at 3.82. The main mineral composition of the high-silicon and high-iron sulfoaluminate cement raw meal after calcination is calcium sulfoaluminate, dicalcium silicate, calcium ferroaluminate, free gypsum, and calcium sulfosilicate. The specific surface area of ​​the high-silicon and high-iron sulfoaluminate cement clinker is controlled at 365 m² / kg.

[0075] The setting time and activity regulator used in this embodiment is calcined gypsum with an SO3 content of 33.40%. The mineral active admixtures are limestone and metakaolin, and the specific surface area of ​​the mineral active admixtures is controlled at 440 m² / kg.

[0076] The intelligent slow-release corrosion inhibitor used in this embodiment is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1.2; specifically, the intelligent slow-release corrosion inhibitor is prepared by mixing β-cyclodextrin and benzotriazole at a molar ratio of 1:1.2, adding 9% acetone by mass of the mixture of β-cyclodextrin and benzotriazole as a reaction aid, and grinding the mixture of acetone, β-cyclodextrin and benzotriazole in a planetary ball mill for 110 min. The resulting paste is then dried at 45°C and 45 Pa vacuum for 12 h to ensure complete reaction, yielding the inclusion complex.

[0077] Example 8 As a preferred embodiment of the present invention, this embodiment provides a low-heat hydration type intelligent slow-release corrosion-resistant cementitious system for marine engineering. By mass percentage, the cementitious system consists of high-silica, high-iron sulfoaluminate cement clinker, accounting for 35% of the total cementitious system; setting time and activity regulator, accounting for 10% of the total cementitious system; mineral active admixture, accounting for 53% of the total cementitious system; and intelligent slow-release corrosion inhibitor, accounting for 2% of the total cementitious system.

[0078] The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then grinding them after calcination at 1290℃.

[0079] High-silica, high-iron sulfoaluminate cement raw meal, by weight, includes: 45 parts of white clay (CaO content 50.20% and SiO2 content 13.80%). 12 portions of sandstone (SiO2=75.30%); 18 parts of aluminum ash slag (Al2O3=66.70%, SiO2=14.50%). Three parts of non-ferrous metal ash slag (Fe2O3=38.90%). 20 parts of fluorinated gypsum (SO3=35.80%); The alkalinity coefficient of the raw meal is 1.00, and the aluminum-sulfur ratio is controlled at 3.0. The main mineral composition of the high-silicon and high-iron sulfoaluminate cement raw meal after calcination is calcium sulfoaluminate, dicalcium silicate, calcium aluminoferrite, free gypsum, and calcium sulfosilicate. The specific surface area of ​​the high-silicon and high-iron sulfoaluminate cement clinker is controlled at 345 m² / kg.

[0080] The setting time and activity regulator used in this embodiment is anhydrite with an SO3 content of 39.60%. The mineral active admixtures are fly ash and slag, and the specific surface area of ​​the mineral active admixtures is controlled at 425 m² / kg.

[0081] The intelligent slow-release corrosion inhibitor used in this embodiment is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1.3; specifically, the intelligent slow-release corrosion inhibitor is prepared by mixing β-cyclodextrin and benzotriazole at a molar ratio of 1:1.3, adding 8% ethanol by mass of the mixture of β-cyclodextrin and benzotriazole as a reaction aid, and grinding the mixture of ethanol, β-cyclodextrin and benzotriazole in a planetary ball mill for 70 min. The ground powder is then dried at 52°C and 20 Pa vacuum for 19 h to ensure complete reaction, resulting in the inclusion complex.

[0082] Comparative Example 1 To highlight the performance proposed in this invention, this comparative example is provided, in which conventional ferroaluminate cement clinker is used instead of high-silica, high-ferroaluminate sulfoaluminate cement clinker as in Example 3 to prepare a cementitious system.

[0083] Comparative Example 2 To highlight the performance proposed in this invention, this comparative example is provided, using the gelling system prepared in Example 3 without the addition of mineral active admixtures.

[0084] Comparative Example 3 To highlight the performance proposed in this invention, this comparative example is provided, using the gelling system prepared in Example 3 without the addition of the intelligent slow-release corrosion inhibitor.

[0085] Experimental Example 1 According to Examples 1-4 and Comparative Examples 1-3 above, the performance of cement was tested in accordance with the relevant provisions of GB / T45920-2025 Aluminoferrite Cement. The test method for the heat of hydration of cement was the isothermal calorimetry method of GB / T12959-2024 Determination of Heat of Hydration of Cement. The specific test results for compressive strength, 28-day free expansion rate and 28-day erosion resistance coefficient are shown in Table 1.

[0086] Table 1 shows the physical performance parameters of the cementitious system.

[0087] According to the data in the table above, under the same technical solution, although the early strength of Examples 1-4 was slightly inferior to the control sample, the strength growth was more stable, and the later strength was significantly better than the control sample. This indicates that during the hydration process, the mineral hydration effect of cementitious clinker and other materials can be reasonably utilized due to the different retarders, mineral admixtures, and intelligent slow-release corrosion inhibitors. By adopting a mineral component design and adjusting the calcium sulfoaluminate content in the clinker, the hydration process of ferroaluminate stabilizes the structure of ettringite crystals. During the iron phase hydration process, iron-containing ettringite is formed, changing the crystal structure of ettringite and enabling it to form dense hydration products in the early stage. Simultaneously, the dicalcium silicate content in the clinker is controlled, and the CSH gel content is coordinated. The ettringite crystals grow in a needle-like and columnar shape, interpenetrating with the CSH gel. The active admixtures are used to form more CSH cement under the alkaline activation of gypsum and alkaline substance hydration products, gradually enhancing the density of the hydration products and improving the resistance to seawater erosion. The standard also has clear provisions for expansion performance, especially the control of anhydrous calcium sulfoaluminate content and adjustment in Example 1. The high alumina slag content of the retarder and active admixture, combined with the dicalcium silicate content, achieves a micro-expansion effect of hydration products. The examples control the clinker mineral composition and the content of active mineral admixtures. Based on the theory of crystallization pressure in supersaturated solutions, the solid phase volume of sulfoaluminate minerals expands due to crystallization pressure. As the minerals formed during clinker hydration and the hydration of active admixtures gradually fill the spaces between ettringite crystals, compensating for the volume shrinkage caused by crystal water loss, the expansion effect is more pronounced compared to the comparative example. In Example 3, which uses high-silicon, high-iron sulfoaluminate clinker, appropriately increasing the dicalcium silicate content reduces the intensity of the hydration reaction of the clinker mineral components. Although the early strength is slightly inferior, it can synergistically hydrate with the active admixtures, thereby reducing the heat release of the hydration reaction compared to the comparative example. This reduces temperature cracks in large-volume concrete caused by temperature rise during construction, thus improving the durability of the concrete. Furthermore, in Example 4, due to the high content of anhydrous calcium sulfoaluminate and the reasonable proportion of active admixtures, the slow-release effect of the intelligent slow-release corrosion inhibitor also improves the cement stone's resistance to seawater ion corrosion.

[0088] For Example 1 Figure 1 Scanning electron microscopy analysis of cement specimens revealed that ettringite crystals grew radially or in bundles, interspersed within the CSH gel matrix. This needle-like crystal structure acts as a "microfiber reinforcement," filling pores and increasing the matrix density. The rough surface of the CSH gel forms flocculent inclusions that surround and intersect the ettringite, creating a continuous cementitious phase. Furthermore, small amounts of aluminum and iron binders fill the voids, further enhancing the density of the structure. Figure 2 and Figure 3In Example 1, the high-silica and high-iron sulfoaluminate cement clinker, compared to ordinary sulfoaluminate cement clinker, exhibits fewer overall clinker pores, and many are spherical. This indicates that the clinker system is not a completely solid-phase reaction in the traditional sense. The high-silica and high-iron components result in a partial liquid phase in the clinker, ensuring a more uniform mineral distribution and a reasonable reaction rate. Early hydration is not intense, while later hydration continues. The anhydrous calcium sulfoaluminate mineral phase particles are small, with a size of 3-10 μm, which is larger than the mineral size (2-3 μm) of ordinary sulfoaluminate cement clinker. This effectively slows down the hydration reaction rate of calcium sulfoaluminate; while the B ore particles are uniform in size and evenly distributed with anhydrous calcium sulfoaluminate ore, with a size between 5μm and 10μm. Compared with the smaller B ore size in ordinary sulfoaluminate cement clinker, this is conducive to the hydration reaction of dicalcium silicate; and there are significantly more white mesophase aluminoferrite minerals, which surround the B ore and anhydrous calcium sulfoaluminate. During the crushing and grinding process, they are easy to grind, providing early hydration reaction aluminate in the cementitious material, and developing in coordination with the hydration reaction rate of calcium sulfoaluminate and dicalcium silicate, thus enhancing the density of cement stone.

[0089] Finally, it should be noted that the above embodiments are merely preferred embodiments of the present invention used to illustrate the technical solutions of the present invention, and are not intended to limit the invention, nor are they intended to limit the patent scope of the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention. That is to say, any changes or refinements made to the main design concept and spirit of the present invention that are not of substantial significance, but whose technical problems are still consistent with the present invention, should be included within the protection scope of the present invention. In addition, the direct or indirect application of the technical solutions of the present invention to other related technical fields are similarly included within the patent protection scope of the present invention.

Claims

1. A low-heat-of-hydration, intelligent, slow-release, corrosion-resistant cementitious system for marine engineering, characterized in that: This cementitious system consists of high-silicon and high-iron sulfoaluminate cement clinker for marine engineering, setting time and activity regulators, mineral active admixtures, and intelligent slow-release corrosion inhibitors. By mass percentage, the amount of the high-silica, high-iron sulfoaluminate cement clinker is 30%-60% of the entire cementitious system; the amount of the setting time and activity regulator is 2%-15% of the entire cementitious system; the amount of the mineral active admixture is 30%-60% of the entire cementitious system; and the amount of the intelligent slow-release corrosion inhibitor is 1%-3% of the entire cementitious system. The high-silicon and high-iron sulfoaluminate cement clinker is made by grinding and pressing high-silicon and high-iron sulfoaluminate cement raw materials mixed in a set ratio into cakes, and then calcining them at a high temperature of 1250℃-1350℃ before grinding. The high-silica, high-iron sulfoaluminate cement raw meal comprises the following components by weight: 40-60 parts calcium-rich material; 2-15 parts of siliceous material; 4-20 parts aluminum material; 0-10 parts of iron material; 10-25 parts of plaster materials; The alkalinity coefficient of the high-silicon, high-iron sulfoaluminate cement raw meal is controlled at 0.95-1.15, and the aluminum-sulfur ratio is controlled at 2.5-3.

82. The high-silicon and high-iron sulfoaluminate cement raw meal is calcined to form a mineral composition including calcium sulfoaluminate, dicalcium silicate, calcium ferroaluminate, free gypsum and calcium sulfosilicate, thus obtaining the high-silicon and high-iron sulfoaluminate cement clinker. The intelligent slow-release corrosion inhibitor is a supramolecular material generated by the inclusion reaction of β-cyclodextrin and benzotriazole; wherein the molar ratio of β-cyclodextrin to benzotriazole is 1:1 to 1:1.

5.

2. The low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in claim 1, characterized in that: The intelligent slow-release corrosion inhibitor is obtained by mixing β-cyclodextrin and benzotriazole in a set ratio, adding reaction aids, and then grinding the resulting mixture in a planetary ball mill. The ground product is then reacted under low-temperature vacuum drying conditions, and the inclusion complex is obtained after the constant reaction is complete.

3. The low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in claim 2, characterized in that: The reaction aid is any one of acetone, ethanol, and water.

4. A low-heat-of-hydration intelligent slow-release corrosion-resistant cementing system for marine engineering as described in claim 2 or 3, characterized in that: The mass ratio of the mixture formed by mixing the reaction aid with β-cyclodextrin and benzotriazole is 5:100-10:

100.

5. The low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in claim 2, characterized in that: The aforementioned low-temperature vacuum drying conditions refer to a temperature of 40℃-60℃ and a vacuum degree of 5pa-50pa.

6. A low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in any one of claims 1-3 or 5, characterized in that: The calcareous material is any one or a mixture of any proportions of conventional limestone, high-silicon limestone, and high-silicon, high-calcium industrial waste residue; the calcareous material contains ≥44.00% CaO and ≤15.00% SiO2.

7. A low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in any one of claims 1-3 or 5, characterized in that: The siliceous material is any one or a combination of sandstone, shale and fluorite washing waste in any proportion, wherein the SiO2 content in the siliceous material is ≥70.00%.

8. A low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in any one of claims 1-3 or 5, characterized in that: The ferrous material is non-ferrous metal ash slag, magnetite, sulfuric acid slag, or copper slag, and the Fe2O3 content in the ferrous material is ≥30.00%; the aluminum material is bauxite, aluminum ash slag, or high-iron bauxite, wherein the Al2O3 content in bauxite is ≥50.00%, and the SiO2 content is ≤20%; the Al2O3 content in aluminum ash slag is ≥65.00%; and the Al2O3 content in high-iron bauxite is ≥50.00%, and the Fe2O3 content is ≥15.00%.

9. A low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in any one of claims 1-3 or 5, characterized in that: The gypsum material is dihydrate gypsum, anhydrite, mixed gypsum, desulfurized gypsum, phosphogypsum, or fluorogypsum, wherein the SO3 content is ≥25%.

10. A low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in any one of claims 1-3 or 5, characterized in that: The specific surface area of ​​the high-silica, high-iron aluminate cement clinker is controlled at 320 m². 2 / kg-380m 2 / kg.

11. A low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in any one of claims 1-3 or 5, characterized in that: The setting time and activity regulator is calcined gypsum, dihydrate gypsum, anhydrite, or a mixture of gypsum, with an SO3 content ≥30%.

12. A low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in any one of claims 1-3 or 5, characterized in that: The active admixture is any two or more of the following materials mixed in any proportion: fly ash, slag, pozzolanic materials, metakaolin, and limestone.

13. The low-heat hydration type intelligent slow-release corrosion-resistant cementing system for marine engineering as described in claim 15, characterized in that: The specific surface area of ​​the active admixture is controlled at 400 m². 2 / kg-450m 2 / kg.

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