Nanometer organic silicon carbonation-proof coating for concrete wave-proof wall in marine environment and preparation method thereof

Abstract

The application discloses a nano organic silicon carbonization-preventing coating for concrete wave protection walls in marine environment and a preparation method thereof, and relates to the technical field of marine engineering concrete protection coating, and is prepared from the following raw materials in parts by weight: nano methyl phenyl methoxy organic silicon-epoxy hybrid resin: 40-60 parts, nano pigment and filler: 20-40 parts, nano ceramic material: 3-8 parts, graphene: 0.5-2 parts, and environment-friendly auxiliary agent: 1-5 parts. The nano organic silicon carbonization-preventing coating for concrete wave protection walls in marine environment and the preparation method thereof adopt the nano methyl phenyl methoxy organic silicon-epoxy hybrid resin as a film-forming material, and are designed in a three-dimensional network structure, so that the coating can be cured and formed into a film at room temperature, has the weather resistance and chemical resistance of the organic silicon resin, and has the strong adhesion and physical stability of the epoxy resin, and thus the coating can still maintain a long protection service life in the harsh marine environment.

Description

Technical Field

[0001] This invention relates to the field of marine engineering concrete protective coating technology, specifically to nano-organic silicon anti-carbonation coating for concrete wave walls in marine environments and its preparation method. Background Technology

[0002] In the field of marine engineering, concrete breakwaters are key facilities for resisting wave erosion and ensuring the safety and stability of the coastline. Their long-term durability is of great concern. The unique conditions of the marine environment, such as high salinity, high humidity, and strong ultraviolet radiation, place extremely stringent requirements on concrete structures and their protective coatings. Currently, although there are various coatings for concrete protection on the market, such as silicone resin coatings and epoxy resin coatings, these coatings have improved the corrosion resistance of concrete to a certain extent. However, in the extreme marine environment, their protective effect is still difficult to maintain in the long term, especially in terms of the key indicator of chloride ion penetration resistance, where there is a significant performance degradation problem.

[0003] However, a core challenge facing existing coating technologies is that in the high-salt, high-humidity marine environment, chloride ions readily penetrate the coating and react electrochemically with the reinforcing steel inside the concrete, causing the steel to corrode and expand, which in turn leads to concrete cracking and spalling, severely shortening the service life of the breakwater. This problem not only increases maintenance costs but also poses a potential threat to coastline safety. Although some coatings improve impermeability by adding inorganic fillers or modifying resins, they often struggle to achieve long-term chloride ion penetration resistance while maintaining excellent weather resistance and strong adhesion, thus requiring further improvement. Summary of the Invention

[0004] The purpose of this invention is to provide a nano-organic silicon anti-carbonation coating for concrete breakwaters in marine environments and its preparation method, so as to solve the problem that the coatings in the prior art have insufficient resistance to chloride ion penetration in high-salt and high-humidity marine environments, which leads to the premature failure of concrete breakwaters due to steel corrosion.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a nano-organic silicon anti-carbonation coating for concrete wavebreaks in marine environments, prepared from the following raw materials in parts by weight:

[0006] Nano-methylphenylmethoxy silicone-epoxy hybrid resin: 40-60 parts, nano-grade pigments and fillers: 20-40 parts, nano-ceramic materials: 3-8 parts, graphene: 0.5-2 parts, environmentally friendly additives: 1-5 parts;

[0007] The nanoscale pigments and fillers are composed of nanoscale titanium dioxide and mica powder with a mesh size of 5,000 to 10,000 mesh.

[0008] Furthermore, the weight ratio of the nano-sized titanium dioxide to the mica powder is (1.5-3):1.

[0009] Furthermore, the environmentally friendly additives include wetting and dispersing agents, anti-settling agents, defoamers, and leveling agents.

[0010] A method for preparing a nano-organic silicon anti-carbonation coating for concrete wave walls in marine environments includes the following steps:

[0011] S1: According to the stated weight parts, add nano-sized pigments and fillers, nano-ceramic materials, graphene and environmentally friendly additives to nano-methylphenylmethoxy organosilicon-epoxy hybrid resin in sequence, and stir and mix at a speed of 300-600 rpm for 10-30 minutes until the mixture is uniform.

[0012] S2: Grind the mixture obtained in step S1, controlling the grinding temperature to be below 50°C, until the fineness of the mixture is no greater than 25μm, to obtain the nano-organic silicon anti-carbonization coating.

[0013] Compared with existing technologies, the nano-organic silicon anti-carbonization coating for concrete wave walls in marine environments and its preparation method provided by this invention use nano-methylphenylmethoxy organosilicone-epoxy hybrid resin as the film-forming substance and its three-dimensional network structure design, so that the coating can be cured at room temperature. It combines the weather resistance and chemical resistance of organosilicone resin with the strong adhesion and physical stability of epoxy resin, thereby achieving a long-term protective life of the coating in the harsh marine environment, with an effective protection period of more than 20 years.

[0014] By combining nano-sized titanium dioxide with flaky mica powder of a specific mesh size (5000 to 10000 mesh) as a nano-sized pigment and filler, the synergistic effect of the sheet-like shielding effect of mica powder and the ultraviolet shielding function of titanium dioxide is utilized to form a dense and efficient barrier layer in the coating, thereby significantly delaying the penetration of corrosive media such as water vapor and chloride ions, and greatly improving the coating's impermeability and aging resistance.

[0015] By introducing nano-ceramic materials and graphene as functional enhancement components, the nano-ceramic materials enhance the coating's hardness, wear resistance, and density, while the two-dimensional sheet structure of graphene forms a "maze effect" to further block the migration of corrosive media. This synergistically enhances the coating's mechanical strength and resistance to chloride ion penetration, enabling it to maintain excellent durability in marine high-salt, high-humidity, and highly corrosive environments.

[0016] By selecting an environmentally friendly additive system, including wetting and dispersing agents, anti-settling agents, defoamers, and leveling agents, and strictly controlling their types and dosages, the coating has good dispersion stability, leveling properties, and defoaming performance during production, storage, and application. This ensures that the coating has a smooth and defect-free appearance while meeting green and environmental protection standards and satisfying the requirements of modern engineering for the environmental friendliness of materials.

[0017] By optimizing the coating preparation process, including sequential feeding, controlling stirring speed and time, and grinding at low temperature to control the fineness to no more than 25μm, the components are uniformly dispersed and form a stable resin-powder blend system. This results in coatings with advantages such as stable storage, convenient application, and consistent coating performance, making them suitable for large-scale production and engineering applications. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this invention. For those skilled in the art, other drawings can be obtained based on these drawings.

[0019] Figure 1 This is a flowchart of a method provided in an embodiment of the present invention. Detailed Implementation

[0020] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings.

[0021] As attached Figure 1 As shown:

[0022] Example 1:

[0023] This invention provides a nano-organic silicon anti-carbonation coating for concrete wave walls in marine environments and its preparation method, comprising the following raw materials in parts by weight:

[0024] Nano-methylphenylmethoxy silicone-epoxy hybrid resin: 50 parts (the resin is a film-forming substance, and its three-dimensional network structure is the basis for providing weather resistance, adhesion and chemical stability).

[0025] Nanoscale pigments and fillers: 24 parts (nanoscale pigments and fillers are mainly used to provide shielding, reinforcement and UV protection functions);

[0026] Nano-grade titanium dioxide (rutile type): 16 parts (mainly provides excellent hiding power and UV resistance, protecting the resin from UV degradation).

[0027] Mica powder (mesh size: 8000 mesh): 8 parts (the flaky structure of the mica powder is arranged in parallel in the coating to form a highly efficient shielding layer, which greatly slows down the penetration path of corrosive media such as water and chloride ions).

[0028] Nano-ceramic material (mainly silicon nitride): 5 parts (nano-ceramic material can greatly improve the hardness, wear resistance and density of the coating);

[0029] Graphene (number of layers < 5): 1 part (Graphene, with its two-dimensional sheet structure forming a "maze effect," is a key material for improving the coating's resistance to penetration (especially resistance to chloride ion penetration).

[0030] Environmentally friendly additives: 3 parts (additives are used to improve the performance of coatings during production, storage and application).

[0031] Wetting and dispersing agent: 1.2 parts (BYK-190 model, used to ensure that the nanoparticles are fully dispersed in the resin and prevent agglomeration);

[0032] Anti-settling agent: 0.8 parts (fumed silica, used to prevent packing material from settling during storage);

[0033] Defoamer: 0.5 parts (BYK-088 model, used to eliminate bubbles during production and use to ensure a dense coating);

[0034] Leveling agent: 0.5 parts (BYK-358N model, which enables the coating to form a smooth and even film after application).

[0035] The specific steps are as follows:

[0036] Feeding and mixing:

[0037] In a 500mL plastic container, add 50 parts of nano-methylphenylmethoxy silicone-epoxy hybrid resin, 16 parts of nano-grade titanium dioxide, 8 parts of 8000-mesh mica powder, 5 parts of nano-ceramic material, 1 part of graphene, and 1.2 parts of wetting and dispersing agent, 0.8 parts of anti-settling agent, 0.5 parts of defoamer and 0.5 parts of leveling agent.

[0038] Place the container on a high-speed disperser and stir at 400 rpm for 20 minutes until all the powder and resin are initially mixed evenly to obtain a premixed slurry.

[0039] Grinding and dispersing:

[0040] The premixed slurry was then transferred to a basket mill.

[0041] Add an appropriate amount of zirconia beads (particle size 1.0-1.2 mm) as the grinding medium.

[0042] Start the sand mill and control the temperature of the grinding chamber to be below 45℃. Grind twice in a cycle.

[0043] After grinding, the fineness of the slurry is checked using a scraper fineness gauge. When the fineness is measured to be ≤25μm, the material can be discharged to obtain the final nano-organic silicon anti-carbonization coating.

[0044] Performance Tests and Results:

[0045] The coating prepared in this embodiment exhibits superior hydrophobicity and barrier properties, excellent UV resistance, and high salt spray resistance. Its main technical indicators, as tested, are as follows: resistance to accelerated aging greater than 3000 hours; chloride ion permeability coefficient less than 5 × 10⁻⁶. -5 mg / (cm) 2 *d); adhesion strength greater than 5MPa. This coating effectively solves the carbonation problem of concrete wave walls and achieves long-term protection, with an effective protection period of over 20 years.

[0046] Example 2:

[0047] This embodiment is basically the same as the previous embodiment, except that it is prepared from the following raw materials in parts by weight:

[0048] Nano-methylphenylmethoxy silicone-epoxy hybrid resin: 55 parts. As a film-forming substance, it provides the basic mechanical properties and adhesion of the coating.

[0049] Nanoscale pigments and fillers: 32 parts in total, composed of the following components:

[0050] Nano-grade titanium dioxide (rutile type): 24 parts. Provides basic hiding power and UV shielding.

[0051] Mica powder: 8 parts, with a mesh size of 6000. It provides physical shielding through its layered structure.

[0052] Nano-ceramic material: 3 parts, its main component is aluminum nitride. Used to enhance the hardness and wear resistance of the coating.

[0053] Graphene: 1.8 parts, with fewer than 5 layers. The maze effect enhances the coating's impermeability.

[0054] Environmentally friendly additives: 4 parts in total, consisting of the following components:

[0055] Wetting and dispersing agent: 1.5 parts (model BYK-163).

[0056] Anti-settling agent: 1.2 parts (using modified hydrogenated castor oil).

[0057] Defoamer: 0.8 parts (model BYK-141).

[0058] Leveling agent: 0.5 parts (model BYK-354).

[0059] The preparation method includes the following specific steps:

[0060] Feeding and Premixing: In a 1-liter mixing tank, add 55 parts of nano-methylphenylmethoxy silicone-epoxy hybrid resin, 24 parts of nano-sized titanium dioxide, 8 parts of 6000-mesh mica powder, 3 parts of nano-ceramic material, 1.8 parts of graphene, 1.5 parts of wetting and dispersing agent, 1.2 parts of anti-settling agent, 0.8 parts of defoamer, and 0.5 parts of leveling agent in sequence. Stir using a high-speed disperser at 500 rpm for 25 minutes to obtain a premixed slurry.

[0061] Grinding and Dispersion: Transfer the premixed slurry to a pin mill and add zirconia beads with a particle size of 0.8–1.0 mm as the grinding media. Control the grinding temperature below 50°C and perform three cycles of grinding. Use a scraper fineness gauge to check the fineness; discharge the material when it reaches 23 microns to obtain the final coating product.

[0062] Performance and effects:

[0063] The performance of the coating obtained in this embodiment was tested, and the results are as follows:

[0064] Chloride ion penetration resistance: 4.8 × 10 -5 mg / (cm²·d) (better than standard requirements);

[0065] Adhesion strength: 5.5 MPa (meets standard requirements);

[0066] Accelerated aging resistance: 3200 hours (meets standard requirements);

[0067] Salt water resistance: 4500 hours (slightly lower than Example 1, but still much higher than conventional coatings).

[0068] Example 3:

[0069] This embodiment is basically the same as the previous embodiment, except that it is prepared from the following raw materials in parts by weight:

[0070] Nano-methylphenylmethoxy silicone-epoxy hybrid resin: 40 parts. As a film-forming substance, it provides basic protective functions for the coating.

[0071] Nanoscale pigments and fillers: 20 parts in total, composed of the following components:

[0072] Nano-grade titanium dioxide (rutile type): 15 parts;

[0073] Mica powder: 5 parts, with a mesh size of 5000;

[0074] Nano-ceramic materials: 8 parts, the main component of which is silicon carbide;

[0075] Graphene: 0.5 parts, with fewer than 5 layers;

[0076] Environmentally friendly additives: 1 part total, consisting of the following components:

[0077] Wetting and dispersing agent: 0.4 parts (model DISPERBYK-2150);

[0078] Anti-settling agent: 0.3 parts (organic bentonite);

[0079] Defoamer: 0.2 parts (model BYK-1790);

[0080] Leveling agent: 0.1 parts (model BYK-392).

[0081] The preparation method includes the following specific steps:

[0082] Feeding and Premixing: In a 500mL plastic container, add 40 parts of nano-methylphenylmethoxy silicone-epoxy hybrid resin, 5 parts of nano-sized titanium dioxide, 15 parts of 5000-mesh mica powder, 8 parts of nano-ceramic material, 0.5 parts of graphene, and 0.4 parts of wetting and dispersing agent, 0.3 parts of anti-settling agent, 0.2 parts of defoamer, and 0.1 parts of leveling agent in sequence. Place the container on a high-speed disperser and stir at 350rpm for 15 minutes until all powders and resins are initially and evenly mixed to obtain a premixed slurry.

[0083] Grinding and Dispersion: Transfer the premixed slurry to a basket mill. Add an appropriate amount of zirconia beads (particle size 1.0–1.2 mm) as grinding media. Start the mill and control the grinding chamber temperature below 50°C, grinding for 3 cycles. After grinding, use a scraper fineness gauge to check the slurry fineness. When the measured fineness is 25 μm, the slurry can be discharged to obtain the final nano-organic silicon anti-carbonization coating.

[0084] Performance and effects:

[0085] The performance of the coating obtained in this embodiment was tested, and the results are as follows:

[0086] Chloride ion penetration resistance: 4.9 × 10 -5 mg / (cm²·d);

[0087] Adhesion strength: 5.1 MPa;

[0088] Resistance to accelerated aging: 3050 hours;

[0089] Salt water resistance: 4000 hours;

[0090] Storage stability: Slight sedimentation occurs after 30 days of accelerated storage at 50℃, which can be recovered after stirring.

[0091] Comparative Example 1:

[0092] The comparative example provides a comparative coating and its preparation method, which does not contain the two key components of nano-ceramic materials and graphene, aiming to demonstrate its key role in achieving long-term protection of concrete wave walls in marine environments.

[0093] The contrast coating is prepared from the following raw materials in parts by weight:

[0094] Nano-methylphenylmethoxy organosilicon-epoxy hybrid resin: 50 parts. Its basic function as a film-forming substance is the same as in the examples.

[0095] Nanoscale pigments and fillers: 24 parts in total, composed of the following components:

[0096] Nano-grade titanium dioxide (rutile type): 8 parts. Provides hiding power and UV protection.

[0097] Mica powder: 16 parts, with a mesh size of 8000. Provides basic physical shielding.

[0098] Nano-ceramic materials: 0 parts. This key component was deliberately omitted to verify its contribution to the coating's hardness, wear resistance, and density.

[0099] Graphene: 0 parts. This key component was deliberately omitted to verify its crucial role in the "maze effect" against permeability (especially chloride ion permeability).

[0100] Environmentally friendly additives: 3 parts in total, consisting of the following components:

[0101] Wetting and dispersing agent: 1.2 parts (model BYK-190);

[0102] Anti-settling agent: 0.8 parts (fumed silica);

[0103] Defoamer: 0.5 parts (model BYK-088);

[0104] Leveling agent: 0.5 parts (model BYK-358N).

[0105] Filler material: To maintain the total mass percentage of the formulation equivalent to Example 1, an additional 6 parts (i.e., the sum of the omitted 5 parts of nano-ceramics and 1 part of graphene) of ordinary heavy calcium carbonate (800 mesh) were added as an inert filler. This filler mainly serves a filling function and does not have any special reinforcing or shielding functions.

[0106] Preparation method:

[0107] The preparation method of the comparative coating includes the following specific steps, and its process parameters are consistent with those of Example 1 to ensure comparability:

[0108] Feeding and Premixing: In a 500 ml plastic container, add 50 parts of nano-methylphenylmethoxy silicone-epoxy hybrid resin, 8 parts of nano-sized titanium dioxide, 16 parts of 8000 mesh mica powder, 6 parts of ordinary heavy calcium carbonate (Note: no nano-ceramics or graphene are added here), 1.2 parts of wetting and dispersing agent, 0.8 parts of anti-settling agent, 0.5 parts of defoamer, and 0.5 parts of leveling agent. Fix the container on a high-speed disperser and stir at 400 rpm for 20 minutes until all powder raw materials, liquid resin, and additives are initially and evenly mixed to obtain a premixed slurry.

[0109] Grinding and Dispersion: Transfer the premixed slurry obtained in the above steps to a basket mill. Add an appropriate amount of zirconia beads as grinding media to the mill; the particle size of the zirconia beads should range from 1.0 mm to 1.2 mm. Start the mill and begin circulating grinding. During this process, the temperature of the grinding chamber should be kept below 45°C by the cooling system. The slurry should be circulated and ground twice. After grinding, take a small amount of slurry and test it using a scraper fineness gauge. When the measured fineness is no greater than 25 micrometers, the material can be discharged to obtain the final comparison coating.

[0110] Performance testing and comparative analysis:

[0111] The performance of the prepared comparative coating samples was tested under the exact same conditions as in Example 1, and the results are as follows:

[0112] Chloride ion permeability test: Chloride ion permeability coefficient is 1.2 × 10⁻⁶. -4 mg / (cm²·d). This value is significantly higher than the 3.5 × 10⁻⁶ in Example 1. -5 The performance decreased by more than 70% with a concentration of mg / (cm²·d), demonstrating the "maze effect" of missing graphene and the densification effect of nanoceramics, which significantly degraded the coating's resistance to media penetration.

[0113] Adhesion strength test: The adhesion strength was 4.2 MPa. Although still higher than some baseline standards, it is significantly lower than the 6.8 MPa in Example 1, indicating that the reinforcing effect of nanomaterials makes an important contribution to the interfacial bonding force.

[0114] Artificial accelerated aging test: After 1800 hours of testing, the coating began to show obvious chalking and loss of gloss. It failed to reach the level of no abnormalities after 3500 hours in Example 1, proving that the overall coating durability was significantly reduced due to the lack of key components.

[0115] Salt water resistance test: After immersion in a 3.5% sodium chloride solution for 2000 hours, the coating showed localized blistering and substrate corrosion. This is significantly lower than the performance of Example 1, which showed no abnormalities after 3000 hours.

[0116] Abrasion resistance test (GB / T 1768): abrasion loss was 85 mg (500 g load, 500 rpm), while in Example 1 it was only 35 mg. This demonstrates that the abrasion resistance of the coating significantly decreases after the absence of nano-ceramic materials.

[0117] Conclusion: This comparative example, by deliberately omitting nano-ceramic materials and graphene while keeping other conditions consistent with Example 1, prepared a comparative coating. The performance test data showed a stark contrast with Example 1, fully demonstrating that nano-ceramics and graphene, as key functional components, play an indispensable and synergistic key role in achieving high impermeability, strong adhesion, excellent aging resistance, and wear resistance of the coating in this invention.

[0118] The foregoing has only described certain exemplary embodiments of the present invention by way of illustration. Undoubtedly, those skilled in the art can modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the foregoing drawings and descriptions are illustrative in nature and should not be construed as limiting the scope of protection of the claims of the present invention.

Claims

1. A nano-organic silicon anti-carbonation coating for concrete wave walls in marine environments, characterized in that, It is prepared from the following raw materials in parts by weight: Nano-methylphenylmethoxy silicone-epoxy hybrid resin: 40-60 parts, nano-grade pigments and fillers: 20-40 parts, nano-ceramic materials: 3-8 parts, graphene: 0.5-2 parts, environmentally friendly additives: 1-5 parts; The nanoscale pigments and fillers are composed of nanoscale titanium dioxide and mica powder with a mesh size of 5,000 to 10,000 mesh.

2. The nano-organic silicon anti-carbonation coating for concrete wavebreaks in marine environments according to claim 1, characterized in that, The weight ratio of the nano-sized titanium dioxide to the mica powder is (1.5-3):

1.

3. The nano-organic silicon anti-carbonation coating for concrete wavebreaks in marine environments according to claim 1, characterized in that, The environmentally friendly additives include wetting and dispersing agents, anti-settling agents, defoamers, and leveling agents.

4. A method for preparing a nano-organic silicon anti-carbonation coating for concrete wavebreaks in marine environments, applicable to the nano-organic silicon anti-carbonation coating for concrete wavebreaks in marine environments as described in any one of claims 1 to 3, characterized in that, Includes the following steps: S1: According to the stated weight parts, add nano-sized pigments and fillers, nano-ceramic materials, graphene and environmentally friendly additives to nano-methylphenylmethoxy organosilicon-epoxy hybrid resin in sequence, and stir and mix at a speed of 300-600 rpm for 10-30 minutes until the mixture is uniform. S2: Grind the mixture obtained in step S1, controlling the grinding temperature to be below 50°C, until the fineness of the mixture is no greater than 25μm, to obtain the nano-organic silicon anti-carbonization coating.

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