A kind of anti-slip coating based on carbon fiber and preparation method thereof

Abstract

The present invention relates to the field of coating materials and provides a carbon fiber-based anti-skid coating and a preparation method thereof. The coating consists of two components, A and B. Component A comprises KH-570 silane coupling agent surface-modified carbon fiber, dog-bone-shaped nano-silica, epoxy-modified hydroxyl acrylic resin, quartz sand anti-skid aggregate, propylene glycol methyl ether acetate, iron oxide pigment and other additives, and component B is an HDI trimer curing agent. The surface-modified carbon fiber is prepared by cleaning and activation, silane coupling agent impregnation, drying and curing, and the like. The dog-bone-shaped nano-silica is prepared by a sol-gel method using hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents. The preparation method includes the steps of preparing iron oxide color paste, dispersing functional components, adding quartz sand, aging treatment and two-component mixing and curing. The coating has excellent dry anti-skid properties, wet anti-skid properties, wear resistance and durability, and is suitable for the field of anti-skid coating on the ground.

Description

Technical Field

[0001] The present invention relates to the field of coating materials, and in particular to an anti-slip coating based on carbon fiber and a preparation method thereof. Background Art

[0002] With the rapid development of modern industry and civil construction, the demand for anti-slip floor coatings in transportation, industrial plants, commercial buildings, public facilities and other fields is growing, especially in places with extremely high safety requirements such as airport runways, port terminals, parking lots, hospital corridors, and food processing workshops. These application scenarios place stringent performance requirements on anti-slip coatings. Not only must they have excellent anti-slip properties to ensure the safe passage of personnel and equipment, they must also have excellent wear resistance to withstand long-term mechanical wear and heavy-load impact. At the same time, the coatings must have good weather resistance, chemical corrosion resistance and service life. Meeting these key performance requirements is of great significance to improving the safety and reliability of floor materials. It can not only effectively reduce the incidence of safety accidents caused by slippery floors and significantly improve the safety of working and living environments, but also extend the service life of floor coatings, reduce maintenance costs, and promote the development of related industries in a safer, more efficient and sustainable direction, providing important material guarantees for building a safe and reliable infrastructure system.

[0003] Although there are many research results in the field of anti-skid coatings, there are still obvious deficiencies in meeting the high performance requirements of practical applications. For example, the Chinese patent publication number CN109439074A discloses an anti-skid coating, but there are problems with insufficient anti-skid and wear-resistant properties. The main reason is that traditional anti-skid coatings mostly adopt a single anti-skid aggregate filling method, lack an effective reinforcing component, which causes the coating to easily fall off the aggregate and suffer from severe surface wear during long-term use. At the same time, the interfacial bonding force between the resin matrix and the anti-skid aggregate in the existing coating system is insufficient, and interfacial peeling easily occurs when subjected to repeated friction and impact loads, thereby affecting the overall anti-skid effect and service life. In addition, the microstructure design of traditional anti-skid coatings is not reasonable enough, and fails to fully utilize the reinforcement effect of nanomaterials and the advantages of surface modification technology, which limits the further improvement of the overall performance of the coating. These technical bottlenecks cause existing anti-skid coatings to be difficult to take into account both excellent anti-skid performance and outstanding wear resistance at the same time, and cannot meet the performance requirements under high-intensity, long-term use environments. Therefore, there is an urgent need to develop new high-performance anti-skid coating technology. Summary of the Invention

[0004] (1) Technical problems solved

[0005] The purpose of the present invention is to provide an anti-skid coating based on carbon fiber and a preparation method thereof, so as to solve the problem that the current coating has insufficient anti-skid and wear-resistant properties.

[0006] (2) Technical solution

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] A carbon fiber-based anti-slip coating, comprising component A and component B, wherein

[0009] a) Component A comprises, by weight: 30.0-40.0 parts of surface modified carbon fiber, 2.0-4.0 parts of dog-bone-shaped nano-silica, 30.0-40.0 parts of epoxy-modified hydroxyl acrylic resin, 18.5-25.0 parts of quartz sand anti-slip aggregate, 10.0-15.0 parts of propylene glycol methyl ether acetate, 15.0-20.0 parts of iron oxide pigment, 1.5-2.5 parts of polyurethane modified polyurea rheological additive, 0.2-0.5 parts of fluorosilicone modified leveling agent, and 0.3-0.5 parts of silicone defoaming agent;

[0010] b) Component B comprises, by weight: 15.0 to 20.0 parts of HDI trimer curing agent;

[0011] c) the surface-modified carbon fiber is a KH-570 silane coupling agent surface-modified carbon fiber;

[0012] d) the dog-bone-shaped nano-silica is prepared by a sol-gel method using hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents;

[0013] e) Components A and B are mixed and cured to form a carbon fiber-based anti-slip coating.

[0014] Furthermore, the surface-modified carbon fiber has an average diameter of 5.0-7.0 μm, an average length of 50.0-100.0 μm, a density of 1.45-1.56 g / cm³, and a tensile strength of 1.8-2.4 GPa.

[0015] Furthermore, the preparation of the surface-modified carbon fiber includes sequentially performing cleaning and activation pretreatment, impregnation with a silane coupling agent hydrolyzate, drying, and heat treatment at 100-110° C. for 30-45 minutes for curing.

[0016] Furthermore, the activation pretreatment step includes: placing the carbon fiber in an ethanol aqueous solution with a mass fraction of 90-95% for ultrasonic cleaning, the ultrasonic frequency is 40-60kHz, and the ultrasonic time is 5-15min, and then soaking the carbon fiber in a dilute nitric acid solution with a mass fraction of 5.0-10% for 20-30min.

[0017] Furthermore, the preparation method of the silane coupling agent hydrolyzate is as follows: dissolving KH~570 at a mass fraction of 1.0~2.5% in a mixed solution of ethanol and deionized water, with a volume ratio of ethanol to water of 6.0~8.0:2.0~4.0, adding acetic acid to adjust the pH value of the solution to 4.0~5.0, stirring at room temperature for 20~30 minutes, and a stirring rate of 200~300 rpm.

[0018] Furthermore, the conditions of the immersion treatment are: heating temperature of 50-60°C, stirring rate of 100-200 rpm, immersion time of 20-25 min, rinsing with ethanol and deionized water for 3.0-5.0 min after immersion, then drying at 60-70°C for 45-60 min, and finally heat treatment and curing at 100-110°C for 30-45 min.

[0019] Furthermore, the preparation method of the dog-bone-shaped nano-silica includes the following steps: dissolving tetraethyl orthosilicate in an ethanol-deionized water mixed solution at a stirring rate of 200.0-300.0 rpm for a stirring time of 15.0-30.0 min to completely dissolve it; adding hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents and continuing to stir for 30.0-60.0 min to fully disperse it; heating at a heating rate of 2.0-5.0°C / min under nitrogen protection and slowly adding ammonia solution dropwise to adjust the pH value at a dropping rate of 0.5-1.5 mL / min; performing a hydrolysis-condensation reaction, detecting the pH value every 60.0-120.0 min during the reaction and adding ammonia solution in time to maintain the pH value stable; cooling, filtering and separating, washing and purifying, drying and heat treating to obtain the dog-bone-shaped nano-silica.

[0020] Furthermore, the preparation of the dog-bone-shaped nano-silica includes the following raw materials in parts by weight: 10.0-15.0 parts by weight of tetraethyl orthosilicate, 80.0-120.0 parts by weight of a mixed solution of ethanol and deionized water in a volume ratio of 3:1, 2.0-5.0 parts by weight of hexadecyltrimethylammonium bromide, 1.0-3.0 parts by weight of polyvinylpyrrolidone, and an ammonia concentration of 3.0-5.0 mol / L.

[0021] The reaction conditions are as follows: a heating rate of 2.0-5.0°C / min, a reaction temperature of 65.0-75.0°C, a stirring rate of 400.0-600.0 rpm, a pH value adjusted to 8.5-9.5 with an aqueous ammonia solution having a concentration of 3.0-5.0 mol / L, a hydrolysis-condensation reaction time of 4.0-8.0 h, a nitrogen protective atmosphere, and a normal pressure.

[0022] Furthermore, the post-treatment step includes: cooling to room temperature at a cooling rate of 3.0~8.0℃ / min, filtering and separating with a polytetrafluoroethylene filter membrane with a pore size of 0.2~0.5μm, washing with deionized water 3~5 times, each washing with 50.0~100.0mL of water, washing with anhydrous ethanol 2~3 times to further remove organic impurities, each washing with 30.0~50.0mL of ethanol, vacuum drying at 80.0~120.0℃ for 12.0~24.0h, with a vacuum degree of -0.08~-0.095MPa, and then heat treating at 400~450℃ for 2.0~4.0h in a nitrogen atmosphere to obtain dog-bone-shaped nano-silica.

[0023] Furthermore, the average length of the dog-bone-shaped nano-silica is 200-800 nm, the diameter of the end spherical region is 70-200 nm, and the diameter of the middle connecting portion is 50-80 nm.

[0024] The present invention adopts the preparation of dog-bone-shaped nano-silica, which is mainly used to enhance the anti-skid performance and wear resistance of anti-skid coatings. Dog-bone-shaped nano-silica has a unique three-dimensional morphology. The special geometric configuration of its end spherical region and middle connecting part provides excellent mechanical reinforcement effect and surface roughness control ability for the coating system. During the preparation process, tetraethyl orthosilicate is used as the silicon source, and the controllable construction of the siloxane network is achieved through the sol-gel method, while hexadecyltrimethylammonium bromide and polyvinylpyrrolidone play a vital role as morphology directing agents. Hexadecyltrimethylammonium bromide, as a cationic surfactant, can guide the orderly assembly of silica precursors through electrostatic and hydrophobic interactions, while polyvinylpyrrolidone further controls the growth direction and morphology evolution of particles through the steric hindrance effect and hydrogen bonding of its molecular chain. The ethanol-deionized water mixed solution not only provides a suitable medium environment for the reaction, but also affects the hydrolysis and condensation kinetics of the precursor through the solvent effect. The nitrogen protective atmosphere effectively avoids oxidative interference during the reaction process, ensuring the purity and structural stability of the product. The precise control of pH value during the hydrolysis and condensation reaction has a decisive influence on the formation of dog-bone morphology. Alkaline conditions promote the rapid condensation of siloxanes, while the coordinated regulation of temperature and stirring rate ensures the uniformity of the reaction and the consistency of the morphology. The washing and purification in the post-treatment step removes the residual organic directing agent and by-products, vacuum drying avoids structural collapse, and high-temperature heat treatment enhances the mechanical strength of silica. The prepared dog-bone-shaped nano-silica has a high specific surface area and a unique morphological structure. When used in combination with surface-modified carbon fibers, it can fill the microscopic defects of the resin matrix at the nanoscale. At the same time, its special dog-bone-shaped structure provides a multi-directional stress transfer path, which complements the linear reinforcement of carbon fibers and constructs a multi-level reinforcement network from nanometers to micrometers, significantly improving the overall mechanical properties of the coating. The hydroxyl functional groups on its surface can also form hydrogen bonds or chemical bonds with epoxy-modified hydroxyl acrylic resins, further enhancing the interfacial bonding strength and achieving a synergistic effect of mechanical enhancement and interface optimization.

[0025] Furthermore, the quality indicators of the epoxy-modified hydroxyl acrylic resin include: hydroxyl content of 3.5% to 4.0%; solid content of 72% to 76%; viscosity of 5000 to 7000 cps;

[0026] The NCO content of the HDI trimer curing agent is 21.0% to 23.0%; the solid content is 71% to 76%.

[0027] The present invention also discloses a method for preparing a carbon fiber-based anti-slip coating, comprising the following steps:

[0028] S1 prepares an iron oxide-based color paste, disperses the functional components, and sequentially adds surface-modified carbon fiber and dog-bone-shaped nano-silica;

[0029] S2 adds quartz sand anti-skid aggregate for dispersion, and adds polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer;

[0030] S3 performs aging treatment to obtain component A, and prepares component B containing HDI trimer curing agent;

[0031] S4: Component A and Component B are mixed and then applied and cured to obtain an anti-slip coating.

[0032] Furthermore, the iron oxide-based color paste in step S1 is prepared as follows: epoxy-modified hydroxy acrylic resin and propylene glycol methyl ether acetate are mixed, dispersed at a speed of 1000~1200 rpm for 5~10 minutes, and then iron oxide pigment is added, dispersed at a speed of 3000~3500 rpm for 10~15 minutes, and then ground with a sand mill to a fineness of less than 30μm; then surface-modified carbon fiber and dog-bone-shaped nano-silica are added in sequence, and dispersed at a speed of 1400~1600 rpm for 25~35 minutes.

[0033] Furthermore, in step S2, quartz sand anti-skid aggregate is added to the above mixture, and dispersed at a speed of 1400-1600 rpm for 25-35 minutes, and then a polyurethane modified polyurea rheological additive, a fluorosilicone modified leveling agent and a silicone defoaming agent are added in sequence, and dispersed at a speed of 1400-1600 rpm for 8-12 minutes while controlling the temperature to be less than 40° C.;

[0034] Furthermore, the aging treatment in step S3 is to seal and age the mixture for 10 to 14 hours and then disperse it at a speed of 1400 to 1600 rpm for 3 to 7 minutes to obtain component A;

[0035] Furthermore, in step S4, component A and component B are mixed and stirred for 5 to 10 minutes and allowed to stand for defoaming for 2 to 5 minutes. An airless spraying process is used for construction, and the wet film thickness is 300 to 400 μm. Under the conditions of 25° C. and relative humidity less than 75%, the surface drying time is 40 to 45 minutes, and the actual drying time is 20 to 28 hours.

[0036] The present invention adopts a two-component system design of epoxy-modified hydroxy acrylic resin and HDI trimer curing agent, which is mainly used to enhance the curing performance and comprehensive mechanical properties of anti-slip coatings. The epoxy-modified hydroxy acrylic resin serves as the main resin, and its molecular structure contains both hydroxyl functional groups and epoxy groups, which provides excellent adhesion and flexibility for the coating system. The moderate hydroxyl content ensures good reactivity with the HDI trimer curing agent, while the reasonable solid content and viscosity range ensure the construction performance and film-forming quality of the coating. The isocyanate groups in the HDI trimer curing agent can undergo a cross-linking reaction with the hydroxyl groups in the hydroxy acrylic resin to form stable urethane bonds, constructing a three-dimensional cross-linked network structure, significantly improving the hardness, wear resistance and chemical corrosion resistance of the coating. Careful design of the preparation process is crucial to achieving the synergistic effects of the various components. During the preparation of the iron oxide color paste, premixing of epoxy-modified hydroxylated acrylic resin and propylene glycol methyl ether acetate provides an excellent medium environment for the dispersion of subsequent components. High-speed dispersion and sand-milling of the iron oxide pigment ensures sufficient wetting and refinement of the pigment, providing the coating with stable coloring and hiding power. The sequential addition of surface-modified carbon fiber and dog-bone-shaped nanosilica employs a graded dispersion strategy to avoid agglomeration and sedimentation between components. The shear force during the high-speed dispersion process promotes the uniform distribution of the fibers and nanoparticles in the resin matrix, forming a stable suspension system. The addition of quartz sand anti-slip aggregate provides the coating with a macroscale anti-slip texture, while the introduction of a polyurethane-modified polyurea rheological additive adjusts the coating's rheological properties and prevents the sedimentation of heavy components. A fluorosilicone-modified leveling agent improves the coating's surface tension and leveling properties, while a silicone defoamer effectively eliminates bubbles generated during the dispersion process. The aging process allows for full wetting and interaction between the components, promoting interfacial bonding and improved system stability. The independent preparation of the HDI trimer curing agent as component B ensures the storage stability and service life of the coating. The application of a two-component hybrid curing system maximizes the performance of the coating. When the surface-modified carbon fiber and dog-bone-shaped nano-silica work synergistically with the two-component resin system, a multi-scale reinforcement network from the molecular level to the macroscopic level is formed. The carbon fiber provides linear reinforcement, the nano-silica achieves microscopic filling and interfacial strengthening, and the two-component curing system builds a matrix network with a high cross-linking density. The synergistic effect of the three far exceeds the sum of the contributions of each single component, significantly improving the coating's anti-slip properties, wear resistance, mechanical strength, and service life, while ensuring excellent construction performance and curing characteristics.

[0037] (3) Beneficial technical effects

[0038] 1. The present invention uses KH-570 silane coupling agent to surface-modify carbon fibers, achieving interfacial chemical bonding and forming a multi-scale reinforcement network with dog-bone-shaped nano-silica. The synergistic effect significantly improves the anti-slip and wear resistance of the coating.

[0039] 2. The present invention uses the unique three-dimensional morphology of dog-bone-shaped nano-silica and the synergistic effect of surface-modified carbon fibers to construct a multi-level reinforcement network, achieving a synergistic effect of mechanical enhancement and interface optimization, significantly improving the anti-slip and wear resistance of the coating.

[0040] 3. The present invention constructs a multi-scale reinforcement network through the synergistic effect of surface-modified carbon fiber, dog-bone-shaped nano-silica and a two-component resin system. It has dry and wet anti-slip properties, as well as good wear resistance and durability, significantly improving the overall performance of the anti-slip coating and solving the technical problem of insufficient anti-slip and wear resistance of existing coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a morphology diagram of the surface-modified carbon fiber prepared in Example 1 of the present invention.

[0042] Figure 2 This is a morphology diagram of the dog-bone-shaped nano-silica prepared in Example 1 of the present invention.

[0043] Figure 3 This is the XRD phase analysis diagram of the dog-bone-shaped nano-silica prepared in Example 1 of the present invention.

[0044] Figure 4 This is a morphology diagram of the dog-bone-shaped nano-silica prepared in Comparative Example 4 of the present invention.

[0045] Figure 5 2 is a comparison chart of the friction coefficients of the embodiments of the present invention and the comparative example.

[0046] Figure 6 The figure is a comparison of the wear resistance of the embodiment of the present invention and the comparative example.

[0047] Figure 7 2 is a comparison chart of the tensile bonding strength of the embodiment of the present invention and the comparative example. DETAILED DESCRIPTION

[0048] To make the objectives, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0049] Example 1

[0050] A carbon fiber-based anti-slip coating, comprising component A and component B, wherein

[0051] a) Component A comprises, by weight: 35.0 parts of surface modified carbon fiber, 3.0 parts of dog-bone-shaped nano-silica, 35.0 parts of epoxy-modified hydroxyl acrylic resin, 21.8 parts of quartz sand anti-slip aggregate, 12.5 parts of propylene glycol methyl ether acetate, 17.5 parts of iron oxide pigment, 2.0 parts of polyurethane modified polyurea rheological additive, 0.35 parts of fluorosilicone modified leveling agent, and 0.4 parts of silicone defoaming agent;

[0052] b) Component B comprises, by weight: 17.5 parts of HDI trimer curing agent;

[0053] c) the surface-modified carbon fiber is a KH-570 silane coupling agent surface-modified carbon fiber;

[0054] d) the dog-bone-shaped nano-silica is prepared by a sol-gel method using hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents;

[0055] e) Components A and B are mixed and cured to form a carbon fiber-based anti-slip coating.

[0056] The surface-modified carbon fibers of this embodiment have an average diameter of 6.0 μm, an average length of 75.0 μm, a density of 1.50 g / cm³, and a tensile strength of 2.1 GPa.

[0057] The preparation of the surface-modified carbon fibers of this embodiment includes sequentially performing cleaning and activation pretreatment, impregnation with a silane coupling agent hydrolyzate, drying, and heat treatment at 105° C. for 37 minutes for curing.

[0058] The activation pretreatment step of this embodiment includes: placing the carbon fiber in a 92% by mass ethanol aqueous solution for ultrasonic cleaning at an ultrasonic frequency of 50 kHz and an ultrasonic time of 10 minutes, and then immersing the carbon fiber in a 7.5% by mass dilute nitric acid solution for 25 minutes.

[0059] The silane coupling agent hydrolyzate of this embodiment was prepared by dissolving KH-570 at a mass fraction of 1.8% in a mixed solution of ethanol and deionized water, with a volume ratio of ethanol to water of 7.0:3.0. Acetic acid was added to adjust the pH of the solution to 4.5, and the mixture was stirred at room temperature for 25 minutes at a stirring rate of 250 rpm.

[0060] The conditions for the immersion treatment in this embodiment are: heating temperature of 55°C, stirring rate of 150 rpm, immersion time of 22 min, rinsing with ethanol and deionized water for 4.0 min after immersion, then drying at 65°C for 52 min, and finally heat treatment and curing at 105°C for 37 min.

[0061] The preparation method of the dog-bone-shaped nano-silica of this embodiment includes the following steps: dissolving tetraethyl orthosilicate in an ethanol-deionized water mixed solution at a stirring rate of 250 rpm for 22 minutes to completely dissolve it; adding cetyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents and continuing to stir for 45 minutes to fully disperse it; heating at a heating rate of 3.5°C / min under nitrogen protection and slowly adding ammonia solution dropwise to adjust the pH value at a dropping rate of 1.0 mL / min; carrying out a hydrolysis-condensation reaction, detecting the pH value every 90 minutes during the reaction and adding ammonia solution in time to maintain the pH value stable; post-processing including cooling, filtration separation, washing purification, drying and heat treatment to obtain the dog-bone-shaped nano-silica.

[0062] The preparation of the dog-bone-shaped nano-silica in this embodiment includes the following raw materials in parts by weight: 12.5 parts by weight of tetraethyl orthosilicate, 100 parts by weight of an ethanol-deionized water mixed solution with a volume ratio of 3:1, 3.5 parts by weight of cetyltrimethylammonium bromide, 2.0 parts by weight of polyvinylpyrrolidone, and an ammonia concentration of 4.0 mol / L; the reaction conditions are: a heating rate of 3.5°C / min, a reaction temperature of 70°C, a stirring rate of 500 rpm, a pH value adjusted to 9.0 with a 4.0 mol / L ammonia solution, a hydrolysis condensation reaction time of 6.0 h, a nitrogen protective atmosphere, and a normal pressure.

[0063] The post-treatment steps of this embodiment include: cooling to room temperature at a cooling rate of 5.5°C / min, filtering and separating with a polytetrafluoroethylene filter membrane with a pore size of 0.35 μm, washing with deionized water four times, each washing with 75 mL of water, washing with anhydrous ethanol twice to further remove organic impurities, each washing with 40 mL of ethanol, vacuum drying at 100°C for 18 h, a vacuum degree of -0.09 MPa, and then heat treating at 425°C for 3.0 h under a nitrogen atmosphere to obtain dog-bone-shaped nano-silica.

[0064] The average length of the dog-bone-shaped nano-silica in this embodiment is 500 nm, the diameter of the spherical region at the end is 135 nm, and the diameter of the middle connecting portion is 65 nm.

[0065] The quality indicators of the epoxy-modified hydroxyl acrylic resin of this embodiment include: hydroxyl content of 3.8%; solid content of 74%; viscosity of 6000 cps;

[0066] The HDI trimer curing agent of this embodiment has an NCO content of 22.0% and a solid content of 73%.

[0067] A method for preparing a carbon fiber-based anti-slip coating according to the present embodiment comprises the following steps:

[0068] S1 prepares iron oxide color paste, disperses functional components, and adds surface modified carbon fiber and dog-bone-shaped nano-silica in sequence; the iron oxide color paste is prepared as follows: epoxy-modified hydroxy acrylic resin and propylene glycol methyl ether acetate are mixed, dispersed at a speed of 1100 rpm for 7 minutes, and then iron oxide pigment is added, dispersed at a speed of 3250 rpm for 12 minutes, and then ground with a sand mill to a fineness of less than 30 μm; then surface modified carbon fiber and dog-bone-shaped nano-silica are added in sequence, and dispersed at a speed of 1500 rpm for 30 minutes.

[0069] S2: adding quartz sand anti-skid aggregate to disperse, adding polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer; adding quartz sand anti-skid aggregate to the above mixture, dispersing at a speed of 1500 rpm for 30 minutes, then adding polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer in sequence, dispersing at a speed of 1500 rpm for 10 minutes while controlling the temperature to be less than 40°C;

[0070] S3 performs a aging treatment to obtain component A, and prepares component B containing an HDI trimer curing agent; the aging treatment comprises sealing and aging the above mixture for 12 hours and then dispersing it at a speed of 1500 rpm for 5 minutes to obtain component A;

[0071] S4: Component A and Component B are mixed and then cured to obtain an anti-slip coating. Component A and Component B are mixed and stirred for 7 minutes and allowed to stand for defoaming for 3 minutes. Airless spraying technology is used for construction. The wet film thickness is 350μm. At 25°C and relative humidity less than 75%, the surface drying time is 42 minutes and the actual drying time is 24 hours.

[0072] Example 1 utilizes a moderate to high content of surface-modified carbon fibers and a moderate content of dog-bone-shaped nano-silica. The surface-modified carbon fibers have medium geometric dimensions and mechanical properties, and the preparation process parameters are selected at medium levels. The dog-bone-shaped nano-silica is prepared using moderate reaction conditions and medium dimensions. The resin system has medium performance indicators, and the preparation process utilizes medium rotational speed and time parameters. The overall formulation design emphasizes stability and operability. This example is suitable for locations with moderate anti-slip requirements and long-term stable use, such as commercial building floors, office building corridors, and light industrial plants. It can provide reliable anti-slip performance and good wear resistance under normal use conditions.

[0073] Example 2

[0074] A carbon fiber-based anti-slip coating, comprising component A and component B, wherein

[0075] a) Component A comprises, by weight: 38.0 parts of surface modified carbon fiber, 2.5 parts of dog-bone-shaped nano-silica, 32.0 parts of epoxy-modified hydroxyl acrylic resin, 23.5 parts of quartz sand anti-slip aggregate, 11.0 parts of propylene glycol methyl ether acetate, 18.5 parts of iron oxide pigment, 1.8 parts of polyurethane modified polyurea rheological additive, 0.25 parts of fluorosilicone modified leveling agent, and 0.45 parts of silicone defoaming agent;

[0076] b) Component B comprises, by weight: 18.5 parts of HDI trimer curing agent;

[0077] c) the surface-modified carbon fiber is a KH-570 silane coupling agent surface-modified carbon fiber;

[0078] d) the dog-bone-shaped nano-silica is prepared by a sol-gel method using hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents;

[0079] e) Components A and B are mixed and cured to form a carbon fiber-based anti-slip coating.

[0080] The surface-modified carbon fibers of this embodiment have an average diameter of 5.5 μm, an average length of 85.0 μm, a density of 1.48 g / cm³, and a tensile strength of 2.3 GPa.

[0081] The preparation of the surface-modified carbon fibers of this embodiment includes sequentially performing cleaning and activation pretreatment, impregnation with a silane coupling agent hydrolyzate, drying, and heat treatment at 108° C. for 33 minutes for curing.

[0082] The activation pretreatment step of this embodiment includes: placing the carbon fiber in a 94% by mass ethanol aqueous solution for ultrasonic cleaning at an ultrasonic frequency of 45 kHz and an ultrasonic time of 8 minutes, and then immersing the carbon fiber in a 6.5% by mass dilute nitric acid solution for 22 minutes.

[0083] The silane coupling agent hydrolyzate of this embodiment was prepared by dissolving KH-570 at a mass fraction of 2.2% in a mixed solution of ethanol and deionized water, with a volume ratio of ethanol to water of 7.5:2.5. Acetic acid was added to adjust the pH of the solution to 4.2, and the solution was stirred at room temperature for 28 minutes at a stirring rate of 280 rpm.

[0084] The conditions for the immersion treatment in this embodiment are: heating temperature of 58°C, stirring rate of 180 rpm, immersion time of 24 min, rinsing with ethanol and deionized water for 3.5 min after immersion, then drying at 68°C for 48 min, and finally heat treatment and curing at 108°C for 33 min.

[0085] The preparation method of the dog-bone-shaped nano-silica of this embodiment includes the following steps: dissolving tetraethyl orthosilicate in an ethanol-deionized water mixed solution at a stirring rate of 280 rpm for 18 minutes to completely dissolve it; adding cetyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents and continuing to stir for 35 minutes to fully disperse it; heating at a heating rate of 2.8°C / min under nitrogen protection and slowly adding ammonia solution dropwise to adjust the pH value at a dropping rate of 0.8 mL / min; carrying out a hydrolysis-condensation reaction, detecting the pH value every 75 minutes during the reaction and adding ammonia solution in time to maintain the pH value stable; post-processing including cooling, filtration separation, washing purification, drying and heat treatment to obtain the dog-bone-shaped nano-silica.

[0086] The preparation of the dog-bone-shaped nano-silica in this embodiment includes the following raw materials in parts by weight: 13.5 parts by weight of tetraethyl orthosilicate, 95 parts by weight of an ethanol-deionized water mixed solution with a volume ratio of 3:1, 2.8 parts by weight of cetyltrimethylammonium bromide, 1.5 parts by weight of polyvinylpyrrolidone, and an ammonia concentration of 4.5 mol / L; the reaction conditions are: a heating rate of 2.8°C / min, a reaction temperature of 67°C, a stirring rate of 450 rpm, a pH value adjusted to 8.8 with a 4.5 mol / L ammonia solution, a hydrolysis condensation reaction time of 5.2 h, a nitrogen protective atmosphere, and a normal pressure.

[0087] The post-treatment steps of this embodiment include: cooling to room temperature at a cooling rate of 4.2°C / min, filtering and separating with a polytetrafluoroethylene filter membrane with a pore size of 0.25 μm, washing with deionized water 5 times, each washing with 65 mL of water, washing with anhydrous ethanol 3 times to further remove organic impurities, each washing with 35 mL of ethanol, vacuum drying at 95°C for 16 h with a vacuum degree of -0.085 MPa, and then heat treating at 410°C for 3.5 h under a nitrogen atmosphere to obtain dog-bone-shaped nano-silica.

[0088] The average length of the dog-bone-shaped nano-silica in this embodiment is 650 nm, the diameter of the spherical region at the end is 165 nm, and the diameter of the middle connecting portion is 58 nm.

[0089] The quality indicators of the epoxy-modified hydroxyl acrylic resin of this embodiment include: hydroxyl content of 3.6%; solid content of 75%; viscosity of 5500 cps;

[0090] The HDI trimer curing agent of this embodiment has an NCO content of 22.5% and a solid content of 74%.

[0091] A method for preparing a carbon fiber-based anti-slip coating according to the present embodiment comprises the following steps:

[0092] S1 prepares iron oxide color paste, disperses functional components, and sequentially adds surface-modified carbon fiber and dog-bone-shaped nano-silica; the iron oxide color paste is prepared as follows: epoxy-modified hydroxy acrylic resin and propylene glycol methyl ether acetate are mixed, dispersed at a speed of 1150 rpm for 6 minutes, and then iron oxide pigment is added, dispersed at a speed of 3400 rpm for 13 minutes, and then ground with a sand mill to a fineness of less than 30 μm; then surface-modified carbon fiber and dog-bone-shaped nano-silica are added sequentially, and dispersed at a speed of 1550 rpm for 28 minutes.

[0093] S2: adding quartz sand anti-skid aggregate to disperse, adding polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer; adding quartz sand anti-skid aggregate to the above mixture, dispersing at a speed of 1550 rpm for 28 minutes, then adding polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer in sequence, dispersing at a speed of 1550 rpm for 9 minutes while controlling the temperature to be less than 40°C;

[0094] S3 performs a aging treatment to obtain component A, and prepares component B containing an HDI trimer curing agent; the aging treatment comprises sealing and aging the above mixture for 11 hours and then dispersing it at a speed of 1550 rpm for 4 minutes to obtain component A;

[0095] S4: Component A and component B are mixed and then cured to obtain an anti-slip coating. Component A and component B are mixed and stirred for 6 minutes and allowed to stand for 4 minutes to defoam. An airless spraying process is used for construction. The wet film thickness is 320 μm. At 25°C and a relative humidity of less than 75%, the surface drying time is 44 minutes and the actual drying time is 22 hours.

[0096] Example 2 uses a higher content of surface-modified carbon fiber and a lower content of dog-bone-shaped nano-silica. The surface-modified carbon fiber has geometric characteristics of smaller diameter and longer length and higher tensile strength. The preparation process uses a higher silane coupling agent concentration and a faster heating rate. The preparation of dog-bone-shaped nano-silica adopts a shorter reaction time and a lower reaction temperature. The resin system has a lower hydroxyl content and a higher NCO content. The preparation process adopts a higher dispersion speed and a shorter aging time. The overall formula tends to strengthen the fiber reinforcement effect. This embodiment is particularly suitable for application scenarios such as airport runways, highway pavements, and heavy-load parking lots that are subjected to high-intensity mechanical loads and frequent wear, and can provide excellent impact resistance and long-term wear resistance.

[0097] Example 3

[0098] A carbon fiber-based anti-slip coating, comprising component A and component B, wherein

[0099] a) Component A comprises, by weight: 32.0 parts of surface modified carbon fiber, 3.5 parts of dog-bone-shaped nano-silica, 38.0 parts of epoxy-modified hydroxyl acrylic resin, 20.0 parts of quartz sand anti-slip aggregate, 14.0 parts of propylene glycol methyl ether acetate, 16.0 parts of iron oxide pigment, 2.2 parts of polyurethane modified polyurea rheological additive, 0.45 parts of fluorosilicone modified leveling agent, and 0.35 parts of silicone defoaming agent;

[0100] b) Component B comprises, by weight: 16.0 parts of HDI trimer curing agent;

[0101] c) the surface-modified carbon fiber is a KH-570 silane coupling agent surface-modified carbon fiber;

[0102] d) the dog-bone-shaped nano-silica is prepared by a sol-gel method using hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents;

[0103] e) Components A and B are mixed and cured to form a carbon fiber-based anti-slip coating.

[0104] The surface-modified carbon fibers of this embodiment have an average diameter of 6.5 μm, an average length of 60.0 μm, a density of 1.53 g / cm³, and a tensile strength of 1.9 GPa.

[0105] The preparation of the surface-modified carbon fibers of this embodiment includes sequentially performing cleaning and activation pretreatment, impregnation with a silane coupling agent hydrolyzate, drying, and heat treatment at 102° C. for 40 minutes for curing.

[0106] The activation pretreatment step of this embodiment includes: placing the carbon fiber in a 91% by mass ethanol aqueous solution for ultrasonic cleaning at an ultrasonic frequency of 55 kHz and an ultrasonic time of 12 minutes, and then immersing the carbon fiber in a dilute nitric acid solution with a mass fraction of 8.5% for 28 minutes.

[0107] The silane coupling agent hydrolyzate of this embodiment was prepared by dissolving KH-570 at a mass fraction of 1.5% in a mixed solution of ethanol and deionized water, with a volume ratio of ethanol to water of 6.5:3.5. Acetic acid was added to adjust the pH of the solution to 4.8, and the solution was stirred at room temperature for 22 minutes at a stirring rate of 220 rpm.

[0108] The conditions for the immersion treatment in this embodiment are: heating temperature of 52°C, stirring rate of 120 rpm, immersion time of 21 min, rinsing with ethanol and deionized water for 4.5 min after immersion, then drying at 62°C for 55 min, and finally heat treatment and curing at 102°C for 40 min.

[0109] The preparation method of the dog-bone-shaped nano-silica of this embodiment includes the following steps: dissolving tetraethyl orthosilicate in an ethanol-deionized water mixed solution at a stirring rate of 220 rpm for 25 minutes to completely dissolve it; adding cetyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents and continuing to stir for 50 minutes to fully disperse it; heating at a heating rate of 4.2°C / min under nitrogen protection and slowly adding ammonia solution dropwise to adjust the pH value at a dropping rate of 1.2 mL / min; carrying out a hydrolysis-condensation reaction, detecting the pH value every 105 minutes during the reaction and adding ammonia solution in time to maintain the pH value stable; post-processing including cooling, filtration separation, washing purification, drying and heat treatment to obtain the dog-bone-shaped nano-silica.

[0110] The preparation of the dog-bone-shaped nano-silica in this embodiment includes the following raw materials in parts by weight: 11.5 parts by weight of tetraethyl orthosilicate, 110 parts by weight of an ethanol-deionized water mixed solution with a volume ratio of 3:1, 4.2 parts by weight of cetyltrimethylammonium bromide, 2.5 parts by weight of polyvinylpyrrolidone, and an ammonia concentration of 3.5 mol / L; the reaction conditions are: a heating rate of 4.2°C / min, a reaction temperature of 73°C, a stirring rate of 550 rpm, a pH value adjusted to 9.3 with a 3.5 mol / L ammonia solution, a hydrolysis condensation reaction time of 7.2 h, a nitrogen protective atmosphere, and a normal pressure.

[0111] The post-treatment steps of this embodiment include: cooling to room temperature at a cooling rate of 6.5°C / min, filtering and separating with a polytetrafluoroethylene filter membrane with a pore size of 0.45 μm, washing with deionized water three times, each washing with 85 mL of water, washing with anhydrous ethanol twice to further remove organic impurities, each washing with 45 mL of ethanol, vacuum drying at 110°C for 14 h, the vacuum degree is -0.092 MPa, and then heat treating at 440°C for 2.5 h under a nitrogen atmosphere to obtain dog-bone-shaped nano-silica.

[0112] The average length of the dog-bone-shaped nano-silica in this embodiment is 350 nm, the diameter of the spherical region at the end is 95 nm, and the diameter of the middle connecting portion is 72 nm.

[0113] The quality indicators of the epoxy-modified hydroxyl acrylic resin of this embodiment include: hydroxyl content of 3.7%; solid content of 73%; viscosity of 6500 cps;

[0114] The HDI trimer curing agent of this embodiment has an NCO content of 21.5% and a solid content of 72%.

[0115] A method for preparing a carbon fiber-based anti-slip coating according to the present embodiment comprises the following steps:

[0116] S1 prepares iron oxide color paste, disperses functional components, and sequentially adds surface-modified carbon fiber and dog-bone-shaped nano-silica; the iron oxide color paste is prepared as follows: epoxy-modified hydroxy acrylic resin and propylene glycol methyl ether acetate are mixed, dispersed at a speed of 1050 rpm for 8 minutes, and then iron oxide pigment is added, dispersed at a speed of 3150 rpm for 14 minutes, and then ground with a sand mill to a fineness of less than 30 μm; then surface-modified carbon fiber and dog-bone-shaped nano-silica are added sequentially, and dispersed at a speed of 1450 rpm for 32 minutes.

[0117] S2: adding quartz sand anti-skid aggregate to disperse, adding polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer; adding quartz sand anti-skid aggregate to the above mixture, dispersing at a speed of 1450 rpm for 32 minutes, then adding polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer in sequence, dispersing at a speed of 1450 rpm for 11 minutes while controlling the temperature to be less than 40°C;

[0118] S3 performs a aging treatment to obtain component A, and prepares component B containing an HDI trimer curing agent; the aging treatment comprises sealing and aging the above mixture for 13 hours and then dispersing it at a speed of 1450 rpm for 6 minutes to obtain component A;

[0119] S4: Component A and Component B are mixed and then cured to obtain an anti-slip coating. Component A and Component B are mixed and stirred for 8 minutes and allowed to stand for 2 minutes to defoam. An airless spraying process is used for construction. The wet film thickness is 380 μm. At 25°C and a relative humidity of less than 75%, the surface drying time is 41 minutes and the actual drying time is 26 hours.

[0120] Example 3 uses a medium-low content of surface-modified carbon fibers and a medium-high content of dog-bone-shaped nano-silica. The surface-modified carbon fibers have geometric characteristics of larger diameter and shorter length. The preparation process uses a lower silane coupling agent concentration and a slower heating rate. The preparation of the dog-bone-shaped nano-silica uses a longer reaction time and a higher reaction temperature. The resin system selects a higher resin content and a higher viscosity. The preparation process uses a lower dispersion speed and a longer aging time. The overall formula focuses on nano-filling and interface optimization effects. This embodiment is mainly suitable for places with special requirements for surface finish and fine anti-slip texture, such as hospital operating rooms, laboratory floors, and food processing workshops. It can provide excellent surface quality and easy-to-clean performance while ensuring anti-slip performance.

[0121] Example 4

[0122] A carbon fiber-based anti-slip coating, comprising component A and component B, wherein

[0123] a) Component A comprises, by weight: 30.5 parts of surface modified carbon fiber, 3.8 parts of dog-bone-shaped nano-silica, 39.0 parts of epoxy-modified hydroxyl acrylic resin, 24.2 parts of quartz sand anti-slip aggregate, 13.5 parts of propylene glycol methyl ether acetate, 19.5 parts of iron oxide pigment, 2.4 parts of polyurethane modified polyurea rheological additive, 0.3 parts of fluorosilicone modified leveling agent, and 0.5 parts of silicone defoaming agent;

[0124] b) Component B comprises, by weight: 19.8 parts of HDI trimer curing agent;

[0125] c) the surface-modified carbon fiber is a KH-570 silane coupling agent surface-modified carbon fiber;

[0126] d) the dog-bone-shaped nano-silica is prepared by a sol-gel method using hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents;

[0127] e) Components A and B are mixed and cured to form a carbon fiber-based anti-slip coating.

[0128] The surface-modified carbon fibers of this embodiment have an average diameter of 5.2 μm, an average length of 95.0 μm, a density of 1.55 g / cm³, and a tensile strength of 2.2 GPa.

[0129] The preparation of the surface-modified carbon fibers of this embodiment includes sequentially performing cleaning and activation pretreatment, impregnation with a silane coupling agent hydrolyzate, drying, and heat treatment at 109° C. for 35 minutes for curing.

[0130] The activation pretreatment step of this embodiment includes: placing the carbon fiber in a 93% by mass ethanol aqueous solution for ultrasonic cleaning at an ultrasonic frequency of 58 kHz and an ultrasonic time of 6 minutes, and then immersing the carbon fiber in a 9.2% by mass dilute nitric acid solution for 26 minutes.

[0131] The silane coupling agent hydrolyzate of this embodiment was prepared by dissolving KH-570 at a mass fraction of 2.4% in a mixed solution of ethanol and deionized water, with a volume ratio of ethanol to water of 6.2:3.8. Acetic acid was added to adjust the pH of the solution to 4.1, and the solution was stirred at room temperature for 26 minutes at a stirring rate of 290 rpm.

[0132] The conditions for the immersion treatment in this embodiment are: heating temperature of 59°C, stirring rate of 190 rpm, immersion time of 23 min, rinsing with ethanol and deionized water for 3.2 min after immersion, then drying at 69°C for 50 min, and finally heat treatment and curing at 109°C for 35 min.

[0133] The preparation method of the dog-bone-shaped nano-silica of this embodiment includes the following steps: dissolving tetraethyl orthosilicate in an ethanol-deionized water mixed solution at a stirring rate of 290 rpm for 20 minutes to completely dissolve it; adding cetyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents and continuing to stir for 55 minutes to fully disperse it; heating at a heating rate of 4.8°C / min under nitrogen protection and slowly adding ammonia solution dropwise to adjust the pH value at a dropping rate of 1.4 mL / min; carrying out a hydrolysis condensation reaction, detecting the pH value every 65 minutes during the reaction and adding ammonia solution in time to maintain the pH value stable; post-processing including cooling, filtration separation, washing purification, drying and heat treatment to obtain dog-bone-shaped nano-silica.

[0134] The preparation of the dog-bone-shaped nano-silica in this embodiment includes the following raw materials in parts by weight: 14.5 parts by weight of tetraethyl orthosilicate, 115 parts by weight of an ethanol-deionized water mixed solution with a volume ratio of 3:1, 4.8 parts by weight of cetyltrimethylammonium bromide, 2.8 parts by weight of polyvinylpyrrolidone, and an ammonia concentration of 4.8 mol / L; the reaction conditions are: a heating rate of 4.8°C / min, a reaction temperature of 74°C, a stirring rate of 580 rpm, a pH value adjusted to 9.4 with a 4.8 mol / L ammonia solution, a hydrolysis condensation reaction time of 7.8 h, a nitrogen protective atmosphere, and a normal pressure.

[0135] The post-treatment steps of this embodiment include: cooling to room temperature at a cooling rate of 7.5°C / min, filtering and separating with a polytetrafluoroethylene filter membrane with a pore size of 0.5 μm, washing with deionized water 5 times, each washing with 95 mL of water, washing with anhydrous ethanol 3 times to further remove organic impurities, each washing with 48 mL of ethanol, vacuum drying at 115°C for 20 h with a vacuum degree of -0.094 MPa, and then heat treating at 445°C for 2.2 h under a nitrogen atmosphere to obtain dog-bone-shaped nano-silica.

[0136] The average length of the dog-bone-shaped nano-silica in this embodiment is 720 nm, the diameter of the spherical region at the end is 185 nm, and the diameter of the middle connecting portion is 55 nm.

[0137] The quality indicators of the epoxy-modified hydroxyl acrylic resin of this embodiment include: hydroxyl content of 3.9%; solid content of 76%; viscosity of 6800 cps;

[0138] The HDI trimer curing agent of this embodiment has an NCO content of 22.8% and a solid content of 75%.

[0139] The method for preparing a carbon fiber-based anti-slip coating of this embodiment includes the following steps:

[0140] S1 prepares iron oxide color paste, disperses functional components, and adds surface modified carbon fiber and dog-bone-shaped nano-silica in sequence; the iron oxide color paste is prepared as follows: epoxy-modified hydroxy acrylic resin and propylene glycol methyl ether acetate are mixed, dispersed at a speed of 1180 rpm for 9 minutes, and then iron oxide pigment is added, dispersed at a speed of 3480 rpm for 11 minutes, and then ground with a sand mill to a fineness of less than 30 μm; then surface modified carbon fiber and dog-bone-shaped nano-silica are added in sequence, and dispersed at a speed of 1580 rpm for 26 minutes.

[0141] S2: adding quartz sand anti-skid aggregate to disperse, adding polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer; adding quartz sand anti-skid aggregate to the above mixture, dispersing at a speed of 1580 rpm for 26 minutes, then adding polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer in sequence, dispersing at a speed of 1580 rpm for 12 minutes while controlling the temperature to be less than 40°C;

[0142] S3 performs a aging treatment to obtain component A, and prepares component B containing an HDI trimer curing agent; the aging treatment comprises sealing and aging the above mixture for 14 hours and then dispersing it at a speed of 1580 rpm for 7 minutes to obtain component A;

[0143] S4: Component A and Component B are mixed and then cured to obtain an anti-slip coating. Component A and Component B are mixed and stirred for 9 minutes and allowed to stand for 5 minutes to defoam. An airless spraying process is used for construction. The wet film thickness is 395 μm. At 25°C and a relative humidity of less than 75%, the surface drying time is 43 minutes and the actual drying time is 27 hours.

[0144] Example 4 uses a surface-modified carbon fiber content close to the lowest and a dog-bone-shaped nano-silica content close to the highest. The surface-modified carbon fiber has geometric characteristics of smaller diameter and longer length, as well as higher density and tensile strength. The preparation process uses a silane coupling agent concentration close to the highest and the fastest heating rate. The dog-bone-shaped nano-silica preparation adopts the highest raw material dosage and the longest reaction time. The resin system selects the highest hydroxyl content and NCO content. The preparation process adopts the highest dispersion speed and the longest aging time. The overall formula pursues the synergistic optimization effect of nano-reinforcement and fiber reinforcement. This embodiment is particularly suitable for application scenarios under extreme environmental conditions such as port terminals, chemical plant areas, and offshore platforms. It can maintain excellent anti-slip and wear resistance for a long time under high humidity, chemical corrosion, and heavy load conditions, while having good environmental adaptability and service life.

[0145] Comparative Example 1: basically the same as Example 1, except that the surface-modified carbon fiber uses original carbon fiber without surface treatment, and the carbon fiber is directly added to component A without surface modification treatment with KH-570 silane coupling agent.

[0146] Comparative Example 2: Basically the same as Example 1, except that the surface-modified carbon fiber is surface-modified using KH-550 silane coupling agent, and the preparation method of the silane coupling agent hydrolyzate is to dissolve KH-550 at a mass fraction of 1.8% in a mixed solution of ethanol and deionized water, and the other preparation conditions remain unchanged.

[0147] Comparative Example 3: Basically the same as Example 1, except that the dog-bone-shaped nano-silica is replaced by spherical nano-silica. The spherical nano-silica is prepared by a sol-gel method without adding a morphology directing agent, and is obtained by directly dissolving tetraethyl orthosilicate in an ethanol-deionized water mixed solution and performing a hydrolysis condensation reaction.

[0148] Comparative Example 4: is basically the same as Example 1, except that only cetyltrimethylammonium bromide is used as a morphology directing agent in the preparation of dog-bone-shaped nano-silica, polyvinylpyrrolidone is not added, and the amount of cetyltrimethylammonium bromide used is 3.5 parts by weight.

[0149] Comparative Example 5: is basically the same as Example 1, except that the heat treatment curing temperature of the surface modified carbon fiber is 80° C., the heat treatment time is 60 min, and the other surface modification treatment conditions remain unchanged.

[0150] Comparative Example 6: basically the same as Example 1, except that the dilute nitric acid solution is replaced by a dilute hydrochloric acid solution in the carbon fiber activation pretreatment step, the mass fraction of the dilute hydrochloric acid solution is 7.5%, and the immersion time is 25 minutes.

[0151] Comparative Example 7: Basically the same as Example 1, except that the pH value of the hydrolysis condensation reaction during the preparation of dog-bone-shaped nano-silica was adjusted to 7.0, the ammonia concentration was 3.5 mol / L, and pH monitoring and replenishment were not performed during the reaction.

[0152] Comparative Example 8: basically the same as Example 1, except that the reaction temperature during the preparation of dog-bone-shaped nano-silica is 45°C, the hydrolysis condensation reaction time is 12h, and the other reaction conditions remain unchanged.

[0153] Comparative Example 9: basically the same as Example 1, except that the post-treatment heat treatment temperature during the preparation of dog-bone-shaped nano-silica is 300°C, the heat treatment time is 6 hours, and the heat treatment is carried out in an air atmosphere.

[0154] Comparative Example 10: basically the same as Example 1, except that the epoxy-modified hydroxyl acrylic resin is replaced by ordinary acrylic resin, and the ordinary acrylic resin has a hydroxyl content of 2.8%, a solid content of 70%, and a viscosity of 4500 cps.

[0155] Comparative Example 11 is basically the same as Example 1, except that the HDI trimer curing agent is replaced by a TDI dimer curing agent, and the NCO content of the TDI dimer curing agent is 18.5%, and the solid content is 68%.

[0156] Comparative Example 12: basically the same as Example 1, except that the volume ratio of the ethanol-deionized water mixed solution in the preparation process of dog-bone-shaped nano-silica was changed to 1:1, the heating rate was 10°C / min, and the stirring rate was 200 rpm.

[0157] Performance testing:

[0158] The dry friction coefficient test for anti-slip coatings, using cured carbon fiber-based anti-slip coatings, evaluates the coating's anti-slip performance under dry conditions. The test principle is based on the friction mechanism between solid surfaces. The coefficient of friction is determined by measuring the ratio of the friction force to the normal load when a standard test block slides over the coating surface. The experimental method uses a portable coefficient of friction tester. A 150 mm × 150 mm × 6 mm anti-slip coating test plate is fixed to a horizontal test table. A standard rubber slider is used as the friction block. The horizontal friction force is measured by dragging the slider at a constant speed under a normal load of 20 N. The test is conducted in accordance with ASTM C1028-07. Key parameters include an ambient temperature of 23 ± 2°C, a relative humidity of 50 ± 5%, a normal load of 20 ± 0.5 N, and a drag speed of 2.5 ± 0.5 mm / s. Data processing is performed by averaging 10 consecutive measurements. The dry friction coefficient must be ≥ 0.55, with a coefficient of variation of less than 10%.

[0159] The wet friction coefficient test experiment of anti-slip coating uses the cured coating of carbon fiber-based anti-slip coating as the test object, with the aim of evaluating the high anti-slip performance of the coating in a humid environment. The test principle is based on the friction characteristics of a wet surface, taking into account the influence mechanism of the water film on the friction interface. The experimental method is based on the dry friction coefficient test. The coating surface is first evenly wetted with deionized water to form a continuous water film with a thickness controlled at 0.5±0.1mm, and then the friction coefficient is measured immediately. The key parameters include ambient temperature of 23±2℃, relative humidity of 85±5%, water film thickness of 0.5±0.1mm, and a test time interval of no more than 30s. The data processing method is to measure each sample 8 times, remove the maximum and minimum values, and take the average value. The wet friction coefficient is required to be ≥0.7, and the reproducibility is limited to within ±0.05.

[0160] The abrasion resistance test for anti-slip coatings, conducted on cured carbon fiber-based anti-slip coatings, aims to evaluate the coating's durability under mechanical wear. The test principle is based on abrasive wear: a standard abrasive is applied to the coating surface in a reciprocating motion under a specified load, and the mass loss before and after wear is measured. A reciprocating abrasion tester was used. A 100 mm × 100 mm × 3 mm coating test panel was mounted on a test bench and subjected to 500 reciprocating cycles of wear using a CS-10 standard abrasive wheel under a load of 750 g. The test was conducted in accordance with GB / T 1768-2006, "Paints and varnishes - Determination of abrasion resistance - Rotating rubber abrasive wheel method." Key parameters included a load of 750 ± 10 g, a rotational speed of 60 ± 2 rpm, a CS-10 abrasive wheel type, a test number of 500 rpm, and an ambient temperature of 23 ± 2°C. Data processing involved weighing the specimens before and after wear using a precision balance. The wear loss was calculated, requiring the wear loss to be ≤ 0.025 g. Changes in the wear track width and depth were also recorded.

[0161] The tensile adhesion strength test of anti-slip coatings is conducted at the interface between a carbon fiber-based anti-slip coating and a substrate, aiming to evaluate the adhesion and interfacial bonding strength between the coating and the substrate. The test principle is based on the stress transfer mechanism at the material interface. A tensile load is applied perpendicular to the coating surface until the interface fails, and the maximum tensile stress is measured. The test method utilizes a pull-off adhesion strength tester. A 1.0±0.1mm thick coating specimen is prepared on a standard concrete substrate. A 50mm standard pull-off head is used to bond the coating to the surface with structural adhesive. After curing for 24 hours, a vertical tensile force is applied at a constant rate until failure. The test standard is based on GB / T 5210-2006. Key parameters include a tensile rate of 1.0±0.1MPa / s, an ambient temperature of 23±2°C, a relative humidity of 50±5%, and a curing time of 24h±1h. Data is processed and recorded, including the maximum tensile load and failure mode, to calculate the tensile adhesion strength, which requires a value of ≥2.5MPa and a cohesive failure rate of ≥80%.

[0162] The artificial weathering resistance test for anti-slip coatings, conducted on cured carbon fiber-based anti-slip coating specimens, aims to evaluate the coating's durability and performance retention under simulated natural weathering conditions. The testing principle is based on the material's aging and degradation mechanisms under cycling of UV light, temperature, and humidity, predicting the material's service life through accelerated weathering testing. The experimental method utilizes a xenon arc artificial weathering chamber. 150mm×70mm×3mm coating test panels are mounted according to standard procedures and subjected to 450 hours of continuous weathering. The aging cycle consists of a 102-minute drying cycle (irradiance 550W / m², black mark temperature 65±3°C) followed by an 18-minute water spray cycle (water temperature 15±5°C). The testing standard is based on GB / T 1865-2009, "Artificial Weathering and Artificial Radiation Exposure of Paints and Varnishes to Filtered Xenon Arc Radiation." Key parameters include an irradiance of 550±50W / m², a black mark temperature of 65±3°C, a relative humidity of 65±5%, an 18-minute water spray cycle, and a total aging time of 450 hours. Data processing: The anti-slip performance and appearance changes are measured before and after the aging test. It is required that the dry friction coefficient remains ≥0.5 after aging, the color difference ΔE ≤2.0, and there are no obvious cracking, peeling and other defects.

[0163] Figure 1 The topography of the surface modified carbon fibers shown confirms the morphology and dispersion of the carbon fibers. Figure 2 The displayed dog-bone-shaped nano-silica morphology image clearly shows the typical dog-bone morphology features, including the spherical regions at both ends and the connecting part in the middle. The morphology has good uniformity and excellent dispersion, proving the successful synergistic effect of the dual morphology directing agents of hexadecyltrimethylammonium bromide and polyvinylpyrrolidone. Figure 3 The XRD phase analysis diagram shows that the dog-bone-shaped nano-silica exhibits typical amorphous silica characteristics, with a broadened diffraction peak appearing around 2θ=22°, indicating that the product is amorphous silica with low crystallinity. This amorphous structure is conducive to compatibility and interfacial bonding with the organic matrix, while maintaining good chemical stability and mechanical properties. Figure 4 The morphology of the nano-silica prepared in Comparative Example 4 shows a significant deviation from the ideal dog-bone structure. The use of only hexadecyltrimethylammonium bromide as a single morphology directing agent results in imperfect particle morphology control, with more irregular shapes and uneven size distribution. Some particles are spherical or ellipsoidal, lacking the typical dog-bone characteristic structure, with a wide particle size distribution and significantly inferior morphology uniformity to that of the product in Example 1. This morphology defect directly affects its reinforcement effect and dispersion stability in the composite material, verifying the importance and technical advantages of the synergistic control of dual morphology directing agents. Figure 5 : This is a comparison chart of the friction coefficients of the embodiments of the present invention and the comparative examples. It can be seen that the dry friction coefficients, wet friction coefficients and dry friction coefficients after aging of the embodiments 1-4 are significantly higher than those of the comparative examples 1-12; Figure 6The figure shows a comparison of the wear resistance of the embodiments of the present invention and the comparative examples, which shows that the wear resistance values ​​of Examples 1-4 are significantly lower than those of Comparative Examples 1-12, and in particular, the wear resistance of Example 3 is only 0.015 g, which shows excellent wear resistance. Figure 7 This is a comparison chart of the tensile bonding strength of the embodiments of the present invention and the comparative examples, showing that the tensile bonding strength of embodiments 1-4 is generally higher than that of comparative examples 1-12, and the tensile bonding strength of embodiment 2 reaches 3.5 MPa, which fully demonstrates the significant effect of the technical solution of the present invention.

[0164] The properties of the coatings of Examples 1 to 4 and Comparative Examples 1 to 12 are summarized in Table 1. As can be seen from the table, the lack of surface modification treatment results in a serious lack of interfacial bonding between the carbon fibers and the resin matrix, low interfacial shear strength, and the fibers are easily pulled out of the matrix, resulting in a significant decrease in tensile bonding strength and wear resistance, and a serious weakening of anti-slip performance. The epoxy group reactivity of the KH-550 silane coupling agent is lower than that of the methacryloyloxy group of KH-570, resulting in relatively weak interfacial chemical bonding. Although various performances have improved, they are still significantly lower than those of the optimized solution. The spherical silica morphology lacks the multi-directional stress transmission ability of the dog-bone structure, has a relatively small specific surface area, and has a weakened mechanical anchoring effect with the matrix, resulting in a significant decrease in anti-slip performance and wear resistance. The use of only a single morphology-directing agent results in imperfect control of the nanosilica morphology, a wide particle size distribution, and poor morphology uniformity, which seriously affects its reinforcement effect and dispersion stability. Low-temperature curing conditions are insufficient to form a complete siloxane network structure, resulting in insufficient interfacial bonding strength, and significantly affecting overall performance. Compared to nitric acid, hydrochloric acid activation is less effective at oxidatively activating the carbon fiber surface, resulting in a lower surface hydroxyl density, which affects the efficiency of the subsequent silane coupling reaction and the quality of interfacial bonding. Under neutral pH conditions, the hydrolysis and condensation rate of the silica precursor is slow, making particle morphology difficult to control and resulting in numerous structural defects in the product, which compromises the ultimate reinforcement effect. Low temperature reaction conditions lead to insufficient reaction kinetics. Despite extended reaction times, product quality remains suboptimal and the expected performance level cannot be achieved. Heat treatment in air leads to oxidative decomposition of surface organic groups, reducing hydrophobicity and, in particular, significantly impacting wet anti-slip properties. Conventional acrylic resins, lacking epoxy groups, exhibit poor compatibility and reactivity with other components, resulting in a lower overall crosslink density and consequently reduced mechanical properties. The reactivity and crosslink density of the TDI dimer curing agent are lower than those of the HDI trimer, significantly reducing the performance of the curing system and impacting the overall quality of the coating. Rapid temperature increases make precise control of the reaction process difficult, resulting in poor product uniformity. Furthermore, an inappropriate alcohol-water ratio also hinders the formation and control of ideal morphology, which collectively impacts the material's ultimate performance.

[0165] Table 1 Summary of the properties of the coatings of Examples 1 to 4 and Comparative Examples 1 to 12

[0166]

[0167] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that any equivalent structural transformations made within the scope of the present invention using the contents of the present invention's description and drawings should be included within the scope of protection of the claims of the present invention.

Claims

1. A carbon fiber-based anti-slip coating, characterized in that: It consists of component A and component B, of which: a) Component A comprises, by weight: 30.0-40.0 parts of surface modified carbon fiber, 2.0-4.0 parts of dog-bone-shaped nano-silica, 30.0-40.0 parts of epoxy-modified hydroxyl acrylic resin, 18.5-25.0 parts of quartz sand anti-slip aggregate, 10.0-15.0 parts of propylene glycol methyl ether acetate, 15.0-20.0 parts of iron oxide pigment, 1.5-2.5 parts of polyurethane modified polyurea rheological additive, 0.2-0.5 parts of fluorosilicone modified leveling agent, and 0.3-0.5 parts of silicone defoaming agent; b) Component B comprises, by weight: 15.0 to 20.0 parts of HDI trimer curing agent; c) the surface-modified carbon fiber is a KH-570 silane coupling agent surface-modified carbon fiber; d) the dog-bone-shaped nano-silica is prepared by a sol-gel method using hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents; e) mixing components A and B and curing them to form a carbon fiber-based anti-slip coating; The preparation of the surface-modified carbon fiber includes sequentially performing cleaning and activation pretreatment, impregnation with a silane coupling agent hydrolyzate, drying, and heat treatment at 100-110°C for 30-45 minutes for curing; The activation pretreatment step comprises: placing the carbon fiber in a 90-95% by mass ethanol aqueous solution for ultrasonic cleaning at an ultrasonic frequency of 40-60 kHz for 5-15 minutes, and then immersing the carbon fiber in a 5.0-10% by mass dilute nitric acid solution for 20-30 minutes; The silane coupling agent hydrolyzate is prepared by dissolving KH-570 at a mass fraction of 1.0-2.5% in a mixed solution of ethanol and deionized water, wherein the volume ratio of ethanol to water is 6.0-8.0:2.0-4.0; adding acetic acid to adjust the pH value of the solution to 4.0-5.0; stirring at room temperature for 20-30 minutes at a stirring rate of 200-300 rpm; The immersion conditions are as follows: heating temperature of 50-60°C, stirring speed of 100-200 rpm, immersion time of 20-25 min, rinsing with ethanol and deionized water for 3.0-5.0 min after immersion, drying at 60-70°C for 45-60 min, and finally heat treatment and curing at 100-110°C for 30-45 min; The preparation method of the dog-bone-shaped nano-silica comprises the following steps: dissolving tetraethyl orthosilicate in an ethanol-deionized water mixed solution at a stirring rate of 200.0-300.0 rpm for a stirring time of 15.0-30.0 minutes to completely dissolve the mixture; adding hexadecyltrimethylammonium bromide and polyvinylpyrrolidone as morphology directing agents and continuing to stir for 30.0-60.0 minutes to fully disperse the mixture; heating the mixture at a heating rate of 2.0-5.0°C / min under nitrogen protection and slowly adding an ammonia solution dropwise to adjust the pH value at a dropping rate of 0.5-1.5 mL / min; performing a hydrolysis-condensation reaction, detecting the pH value every 60.0-120.0 minutes during the reaction process and adding ammonia solution in a timely manner to maintain a stable pH value; and subsequent processing comprising cooling, filtering and separating, washing and purifying, drying, and heat treatment to obtain the dog-bone-shaped nano-silica. The preparation of the dog-bone-shaped nano-silica comprises the following raw materials in parts by weight: 10.0 to 15.0 parts by weight of tetraethyl orthosilicate, 80.0 to 120.0 parts by weight of a mixed solution of ethanol and deionized water in a volume ratio of 3:1, 2.0 to 5.0 parts by weight of hexadecyltrimethylammonium bromide, 1.0 to 3.0 parts by weight of polyvinylpyrrolidone, and an ammonia concentration of 3.0 to 5.0 mol / L. The specific conditions of the hydrolysis and condensation reaction are as follows: a heating rate of 2.0 to 5.0°C / min, a reaction temperature of 65.0 to 75.0°C, a stirring rate of 400.0 to 600.0 rpm, a pH value adjusted to 8.5 to 9.5 with an aqueous ammonia solution having a concentration of 3.0 to 5.0 mol / L, a hydrolysis and condensation reaction time of 4.0 to 8.0 h, a nitrogen protective atmosphere, and a normal pressure. The subsequent treatment steps include: cooling to room temperature at a cooling rate of 3.0-8.0°C / min, filtering and separating with a polytetrafluoroethylene filter membrane with a pore size of 0.2-0.5 μm, washing with deionized water 3-5 times, each washing with 50.0-100.0 mL of water, washing with anhydrous ethanol 2-3 times to further remove organic impurities, each washing with 30.0-50.0 mL of ethanol, vacuum drying at 80.0-120.0°C for 12.0-24.0 hours, with a vacuum degree of -0.08-0.095 MPa, and then heat treating at 400-450°C for 2.0-4.0 hours in a nitrogen atmosphere to obtain dog-bone-shaped nano-silica.

2. The carbon fiber-based anti-slip coating according to claim 1, characterized in that: The surface-modified carbon fibers have an average diameter of 5.0 to 7.0 μm, an average length of 50.0 to 100.0 μm, a density of 1.45 to 1.56 g / cm³, and a tensile strength of 1.8 to 2.4 GPa.

3. The carbon fiber-based anti-slip coating according to claim 1, wherein: The average length of the dog-bone-shaped nano-silica is 200-800 nm, the diameter of the spherical region at the end is 70-200 nm, and the diameter of the middle connecting part is 50-80 nm; The quality indicators of the epoxy-modified hydroxyl acrylic resin include: hydroxyl content of 3.5% to 4.0%; solid content of 72% to 76%; viscosity of 5000 to 7000 cps; The NCO content of the HDI trimer curing agent is 21.0% to 23.0%; the solid content is 71% to 76%.

4. The method for preparing a carbon fiber-based anti-slip coating according to any one of claims 1 to 3, wherein: The following steps are involved: S1 prepares an iron oxide-based color paste, disperses the functional components, and sequentially adds surface-modified carbon fiber and dog-bone-shaped nano-silica; S2 adds quartz sand anti-skid aggregate for dispersion, and adds polyurethane modified polyurea rheological additive, fluorosilicone modified leveling agent and silicone defoamer; S3 performs aging treatment to obtain component A, and prepares component B containing HDI trimer curing agent; S4: Component A and Component B are mixed and then applied and cured to obtain an anti-slip coating.

5. The method for preparing a carbon fiber-based anti-slip coating according to claim 4, wherein: The following steps are involved: The iron oxide color paste in step S1 is prepared by mixing epoxy-modified hydroxy acrylic resin and propylene glycol methyl ether acetate, dispersing them at a speed of 1000-1200 rpm for 5-10 minutes, adding iron oxide pigment, dispersing them at a speed of 3000-3500 rpm for 10-15 minutes, and then grinding them with a sand mill to a fineness of less than 30 μm; then adding surface-modified carbon fiber and dog-bone-shaped nano-silica in sequence, and dispersing them at a speed of 1400-1600 rpm for 25-35 minutes to obtain a functional component mixture; Furthermore, in step S2, quartz sand anti-skid aggregate is added to the functional component mixture, dispersed at a speed of 1400-1600 rpm for 25-35 minutes, and then a polyurethane modified polyurea rheological additive, a fluorosilicone modified leveling agent and a silicone defoamer are added in sequence, dispersed at a speed of 1400-1600 rpm for 8-12 minutes and the temperature is controlled to be less than 40° C. to obtain a premixture; The aging treatment in step S3 is to seal and age the premix for 10 to 14 hours and then disperse it at a speed of 1400 to 1600 rpm for 3 to 7 minutes to obtain component A; In step S4, component A and component B are mixed and stirred for 5 to 10 minutes and allowed to stand for defoaming for 2 to 5 minutes. The airless spraying process is used for construction, and the wet film thickness is 300 to 400 μm. Under the conditions of 25° C. and relative humidity less than 75%, the surface drying time is 40 to 45 minutes, and the actual drying time is 20 to 28 hours.

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