An anti-slip inorganic zinc coating and its preparation method

Abstract

This invention discloses an anti-slip inorganic zinc coating and its preparation method, belonging to the field of functional protective coating technology. The anti-slip inorganic zinc coating comprises the following raw materials in parts by weight: 65-75 parts zinc powder, 6-10 parts titanium dioxide, 6-8 parts mica powder, 18-22 parts deionized water, 15-20 parts isopropanol, 3-5 parts ethylene glycol, 12-18 parts modified wollastonite, 4-6 parts fumed silica, 2-4 parts silica-coated aluminum powder, 18-22 parts modified zinc phosphate, 28-32 parts tetraethyl orthosilicate, 5-7 parts phosphoric acid, and 4-6 parts zinc nitrate. This anti-slip inorganic zinc coating and its preparation method have significant advantages. The raw material ratio is scientific; the zinc powder is degreased, and the aluminum powder is coated to improve performance; the modified zinc phosphate and modified wollastonite are prepared using refined processes, enhancing the coating's stability. The preparation process involves staged temperature and speed control, and the grinding and filtration stages are rigorous, ensuring uniform particle size and suitable viscosity of the coating. The final coating exhibits excellent anti-slip and anti-corrosion properties and is widely applicable.

Description

Technical Field

[0001] This invention relates to the field of functional protective coatings, specifically to an anti-slip inorganic zinc coating and its preparation method. Background Technology

[0002] In the field of industrial corrosion protection and functional protection, inorganic zinc coatings are widely used in bridges, marine engineering, oil storage tanks, steel structures, and other applications due to their excellent corrosion resistance, high-temperature resistance, and environmental friendliness. However, traditional inorganic zinc coatings still have many technical limitations in practical applications, making it difficult to meet the anti-slip and long-term protection requirements under complex working conditions.

[0003] On the one hand, the anti-slip performance of traditional inorganic zinc coatings relies on the addition of a single aggregate, such as ordinary quartz sand or talc. These aggregates have poor compatibility with the coating matrix and are prone to sedimentation and agglomeration, resulting in uneven surface roughness and unstable anti-slip effect. Especially in humid or oily environments, the coefficient of friction drops significantly, which can easily lead to safety accidents such as people slipping or equipment sliding.

[0004] On the other hand, the corrosion resistance of traditional products is significantly constrained by the characteristics of raw materials. Unmodified zinc powder is prone to insufficient bonding with film-forming substances due to surface oil and oxide layers, resulting in pinholes and cracks in the coating. Corrosion inhibitors such as zinc phosphate have poor dispersibility and cannot exert a uniform corrosion inhibition effect, leading to a shortened protective life of the coating in salt spray and acid / alkali environments, requiring frequent recoating and increasing maintenance costs.

[0005] Meanwhile, traditional preparation processes have drawbacks. For example, improper temperature control during grinding can damage the activity of raw materials, and uneven material dispersion during mixing can lead to fluctuations in coating performance. The final product's viscosity and particle size are difficult to adapt to different application methods, such as spraying and brushing, affecting application efficiency and coating quality. Furthermore, some coatings add toxic additives to enhance performance, which does not meet modern environmental protection requirements and limits their application in food processing, drinking water facilities, and other fields.

[0006] Therefore, developing an inorganic zinc coating that features reasonable raw material modification, precise preparation process, stable anti-slip properties, long-lasting anti-corrosion properties, and meets environmental protection standards has become a key need to address the current pain points in the industry. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides an anti-slip inorganic zinc coating and its preparation method, which solves the problems of unstable anti-slip performance, short anti-corrosion life, easy sedimentation of the system, and insufficient environmental friendliness of traditional inorganic zinc coatings.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] An anti-slip inorganic zinc coating comprises the following raw materials in parts by weight: 65-75 parts zinc powder, 6-10 parts titanium dioxide, 6-8 parts mica powder, 18-22 parts deionized water, 15-20 parts isopropanol, 3-5 parts ethylene glycol, 12-18 parts modified wollastonite, 4-6 parts fumed silica, 2-4 parts silica-coated aluminum powder, 18-22 parts modified zinc phosphate, 28-32 parts tetraethyl orthosilicate, 5-7 parts phosphoric acid, and 4-6 parts zinc nitrate.

[0010] Furthermore, the zinc powder has a particle size of 10-20 μm and undergoes surface degreasing treatment. The specific steps of the degreasing treatment are as follows: add the zinc powder to an 8% sodium hydroxide solution and stir at 250 r / min for 20 min at 45°C to thoroughly remove oil and oxide layers from the surface of the zinc powder, preventing oil from affecting the bonding force between the zinc powder and the film-forming substance; then wash with deionized water until neutral and dry in a forced-air dryer at 95°C for 3 h to prevent residual alkali from damaging the stability of the coating system, ultimately improving the electrochemical activity of the zinc powder and enabling it to more efficiently perform the anti-corrosion function of the sacrificial anode.

[0011] Furthermore, the silica-coated aluminum powder is in the form of flake aluminum powder with a diameter-to-thickness ratio of 50-80:1, and its surface is coated with a 2% by mass silica protective film. This film can isolate the aluminum powder from contact with air and moisture, preventing the aluminum powder from oxidizing and failing. At the same time, the flake structure, together with the protective film, can build a three-dimensional support structure within the coating, enhancing the surface friction coefficient and mechanical strength of the coating. The protective film is prepared as follows: 100g of aluminum powder is dispersed in 500mL of a 3:1 volume ratio ethanol-water mixed solution, 0.5g of silane coupling agent KH-550 is added, and the mixture is stirred at 30℃ for 30min. Then, a mixture of 6g of tetraethyl orthosilicate and 1.2mL of hydrochloric acid with a pH of 4.5 is added dropwise. The temperature is controlled at 50℃ and the reaction is carried out at 300r / min for 2h, and then the temperature is raised to 80℃ and the reaction is carried out for 1h. After centrifugation and washing, the mixture is vacuum dried at 60℃ for 2h.

[0012] Furthermore, the modified zinc phosphate is prepared using the following specific steps:

[0013] A1. Weigh zinc phosphate and place it in a beaker. Add deionized water and stir with a magnetic stirrer at 300-350 rpm for 20-30 minutes to form a uniform suspension. Measure silane coupling agent KH-560 and lignin, add ethanol, and ultrasonically disperse with 250W for 10-20 minutes to prepare a modifier solution. Pour the modifier solution into the suspension and stir at 350-400 rpm for 2.5-3.5 hours in a constant temperature water bath at 60-70℃. This can improve the compatibility of zinc phosphate with the coating matrix and prevent zinc phosphate agglomeration. The constant temperature water bath reaction can promote the full bonding of the modifier with the surface of zinc phosphate and initially improve its dispersibility. Then filter with a Buchner funnel. Wash the filter cake 3-4 times with a 1:1 volume ratio ethanol-water mixture. Finally, vacuum dry at 75-85℃ for 4-5 hours to obtain the first modified zinc phosphate.

[0014] A2. Take the first modified zinc phosphate, add anhydrous ethanol, and ultrasonically disperse it in a three-necked flask at 300W for 20-25 minutes to form a stable dispersion. Add tetraethyl orthosilicate dropwise at a rate of 1 drop / second to form a dense siloxane coating layer on the surface of zinc phosphate, enhancing its acid and alkali resistance. Simultaneously add 1 mol / L hydrochloric acid to adjust the pH to 3-4, maintain stirring at 300 rpm, and reflux at 68-72℃ for 3-4 hours. After cooling, centrifuge for 15 minutes, wash the precipitate 3-4 times with anhydrous ethanol, dry it at 105-115℃ for 3.5-4.5 hours, and then pass it through a 200-mesh sieve to obtain the second modified zinc phosphate. Sieving controls the particle size of the modified zinc phosphate to be uniform, avoiding fluctuations in coating performance caused by particle size differences.

[0015] A3. Weigh the second batch of modified zinc phosphate, add deionized water and stir to form a suspension. Add lanthanum nitrate and stir until completely dissolved. Add 10% (w / w) ammonia water to adjust the pH to 8.5-9.5. Heat to 80-90℃ and maintain the temperature for 2-3 hours. After filtration, wash the filter cake with deionized water until neutral. Place it in a muffle furnace and calcine at 380-420℃ at a rate of 4-6℃ / min for 1.2-1.8 hours. After natural cooling, the modified zinc phosphate is obtained. Lanthanum nitrate can form a composite corrosion inhibitor with zinc phosphate, improving corrosion inhibition efficiency. Gradient heating can prevent structural cracking of zinc phosphate due to sudden temperature rise, ultimately allowing the modified zinc phosphate to be uniformly dispersed and forming a dense passivation film, blocking the penetration of corrosion ions.

[0016] Furthermore, in the A1 suspension, the ratio of zinc phosphate to deionized water is 20g:35-45mL; and in the modifier solution, the ratio of silane coupling agent KH-560, lignin, and ethanol is 7-9mL:2.5-3.5g:4-6mL.

[0017] Furthermore, the ratio of the first modified zinc phosphate, anhydrous ethanol, and tetraethyl orthosilicate in A2 is 20g: 50-60mL: 11-13mL.

[0018] Furthermore, the ratio of the second modified zinc phosphate, deionized water, and lanthanum nitrate in A3 is 20g: 25-35mL: 3.5-4.5g.

[0019] In A1, the silane coupling agent KH-560 contains epoxy groups, which can react with the hydroxyl groups on the surface of zinc phosphate to form chemical bonds. Lignin, on the other hand, adheres to the surface of zinc phosphate through adsorption. The two work synergistically to improve the compatibility of zinc phosphate with the coating matrix, avoid agglomeration, and lay the foundation for subsequent modification.

[0020] In A2, tetraethyl orthosilicate hydrolyzes under acidic conditions to generate siloxanes, which uniformly coat the surface of zinc phosphate to form a dense layer, enhancing its acid and alkali resistance. At the same time, it further optimizes dispersibility to ensure uniform distribution in the coating.

[0021] In A3, lanthanum nitrate reacts with zinc phosphate to form a composite corrosion inhibitor. After gradient heating and calcination, the composite component can be fixed and the zinc phosphate structure can be prevented from cracking, ultimately improving the corrosion inhibition efficiency. It can also react with the metal substrate to form a dense passivation film to block corrosion ions.

[0022] Furthermore, the modified wollastonite is prepared using the following specific steps:

[0023] B1. Weigh wollastonite and place it in a beaker. Add a mixed acid consisting of hydrochloric acid and citric acid. Stir the mixture at 300-350 r / min for 4.5-5.5 h in a constant temperature water bath at 78-82℃. After filtration, wash the filter cake with deionized water until pH=7. Vacuum dry at 70-80℃ for 4.5-5.5 h to obtain the first modified wollastonite. The mixed acid can etch the surface of wollastonite to form a rough and porous structure, increasing its contact area with the coating substrate and laying the foundation for subsequent modification. Washing with water to neutral and vacuum drying can remove residual acid and prevent abnormal pH of the coating.

[0024] B2. Take the first-modified wollastonite, add deionized water and ultrasonically disperse it for 20-30 minutes at 300W power. Transfer it to a four-necked flask, add styrene, butyl acrylate, and ammonium persulfate, and stir at 300-350 r / min at 73-77℃ for 3.5-4.5 hours under nitrogen protection to avoid monomer oxidation and ensure the stable progress of the grafting reaction. After cooling, centrifuge for 15 minutes, wash the precipitate 2-3 times with deionized water, dry it at 95-105℃ for 4-5 hours, and then pass it through a 300-mesh sieve to obtain the second-modified wollastonite. Ultrasonic dispersion can make the grafted polymer adhere evenly to the surface of wollastonite, further improving the compatibility of wollastonite with the inorganic film-forming system and reducing sedimentation.

[0025] B3. Take the second modified wollastonite, add deionized water and stir to form a suspension. Add 0.8 mol / L barium chloride solution dropwise and stir for 8-12 min. Add 0.8 mol / L sodium sulfate solution dropwise over 14-16 min. Stir at 250-300 r / min at 28-32℃ for 1.8-2.2 h. After the reaction, filter and wash the filter cake with deionized water until no chloride ions are detected in the filtrate. Finally, dry in a forced-air environment at 85-95℃ for 3.5-4.5 h to obtain modified wollastonite. The addition of barium chloride and sodium sulfate can form barium sulfate microparticles on the surface of wollastonite, increasing the surface roughness of wollastonite. Combined with its fibrous structure, it can construct "micro-protrusion" anti-slip units on the coating surface, significantly improving anti-slip performance.

[0026] Furthermore, the ratio of wollastonite to mixed acid in B1 is 15g:170-190mL; wherein the mixed acid is prepared by 135-145mL of 10% hydrochloric acid and 35-45mL of 5% citric acid.

[0027] Furthermore, the ratio of the first modified wollastonite, deionized water, styrene, butyl acrylate, and ammonium persulfate in B2 is 15g: 110-130mL: 3-4mL: 2-3mL: 0.7-0.9g.

[0028] Furthermore, the ratio of the amount of the second modified wollastonite, deionized water, barium chloride solution, and sodium sulfate solution in B3 is 15g:75-85mL:18-22mL:17-19mL.

[0029] The mixed acid prepared by B1 with 10% hydrochloric acid and 5% citric acid can selectively dissolve impurities and some components on the surface of wollastonite, forming a rough and porous surface, increasing the specific surface area and active sites, and creating conditions for subsequent organic grafting.

[0030] In B2, under nitrogen protection, ammonium persulfate initiates the polymerization reaction of styrene and butyl acrylate on the surface of wollastonite to form an organic graft layer, which greatly improves the compatibility of wollastonite with the inorganic film-forming system and reduces sedimentation during storage.

[0031] In B3, barium chloride and sodium sulfate react on the surface of wollastonite to generate barium sulfate microparticles. After uniform coating, the surface roughness of wollastonite is increased. Combined with its fibrous structure, "micro-protrusions" are built on the coating surface to form anti-slip units, which significantly enhances the anti-slip performance.

[0032] A method for preparing an anti-slip inorganic zinc coating specifically includes the following steps:

[0033] S1. Dry zinc powder, titanium dioxide, and mica powder at 100-110℃ for 2-3 hours; activate fumed silica at 120-130℃ for 1-2 hours to enhance its thixotropic properties and prevent solid particles from settling when standing.

[0034] S2. Add 18-22 parts of deionized water, 12-16 parts of isopropanol, and 3-5 parts of ethylene glycol to the dispersion vessel, and stir at 500-600 r / min for 5-10 min. Then, add 65-75 parts of zinc powder, 6-10 parts of titanium dioxide, 6-8 parts of mica powder, 4-6 parts of fumed silica, and 2-4 parts of silica-coated aluminum powder in sequence. Stir for 15-20 min after each addition of raw material to ensure uniform dispersion and avoid excessively high local concentrations. Finally, add 18-22 parts of modified zinc phosphate and 12-18 parts of modified wollastonite, and stir for 30-40 min to prepare component A.

[0035] S3. Add 28-32 parts of tetraethyl orthosilicate to another reactor, stir at 300-400 r / min, slowly add 5-7 parts of phosphoric acid dropwise over 20-30 min, keep the temperature at 25-30℃, continue stirring for 1-1.5 h, then add 4-5 parts of zinc nitrate, stir for 10-15 min to prepare component B.

[0036] Components S4 and B are added to component A at a rate of 1 mL / s, and stirred at 600-700 r / min for 30-35 min to ensure uniform mixing. Then, the mixture is transferred to a sand mill, and 1 mm diameter zirconium beads are added at a mass ratio of 3:1 to the system. The mixture is then ground at 1500-1800 r / min for 2-2.5 h to control the particle size at 7-9 μm. The mixture is then filtered using a 150 μm filter bag to ensure uniform particle size, making it suitable for spraying, brushing, and other application methods, and preventing fluctuations in the anti-slip and anti-corrosion properties of the coating due to uneven particle size. After filtration, the viscosity is tested at 25°C using a Ford cup 4, adjusted to 60-70 s with isopropanol, and the pH is adjusted to 4-5 with phosphoric acid to obtain the anti-slip inorganic zinc coating.

[0037] Furthermore, during the grinding process of the sand mill, a segmented temperature control method is adopted. The temperature is controlled at 25-30℃ in the first hour and then at 30-35℃. This can protect the initial properties of the material and improve the grinding efficiency and particle size uniformity in the later stage, ultimately ensuring the stability of the coating system and its core properties such as anti-slip and anti-corrosion.

[0038] This invention provides an anti-slip inorganic zinc coating and its preparation method, which has the following beneficial effects:

[0039] 1. This invention endows coatings with superior and durable anti-slip capabilities through multi-component synergistic optimization and structural design. From the perspective of raw material selection, modified wollastonite, after mixed acid etching, organic monomer grafting, and barium sulfate coating, forms a rough, porous composite structure on its surface. This not only enhances the bonding strength with the coating matrix but also constructs uniformly distributed "micro-protrusions" anti-slip units on the coating surface. Simultaneously, flake-shaped silica-coated aluminum powder and fumed silica are synergistically dispersed, forming a three-dimensional interwoven support structure within the coating, further enhancing the surface friction coefficient. Compared to traditional coatings that rely on single aggregates and suffer from easy settling and fluctuating anti-slip effects, the combination of modified wollastonite, silica-coated aluminum powder, and fumed silica in this invention avoids aggregate agglomeration or detachment. Even in harsh environments such as dampness and oil contamination, it maintains stable anti-slip performance, effectively reducing the safety risks of slipping and equipment slippage. It is suitable for scenarios with stringent anti-slip requirements, such as bridges, offshore platforms, and industrial workshop floors.

[0040] 2. The coating system utilizes multiple anti-corrosion mechanisms to construct a long-lasting protective barrier. The core anti-corrosion component, zinc powder, undergoes surface degreasing treatment to remove surface oil and oxide layers, enhancing its dispersibility and electrochemical activity in the coating and enabling it to more effectively perform sacrificial anodic protection. Modified zinc phosphate not only exhibits significantly improved dispersibility, allowing for uniform distribution within the coating, but also reacts with the metal substrate surface to form a dense phosphate passivation film, blocking the penetration of moisture, oxygen, and corrosive ions. Simultaneously, the inorganic film-forming system formed by tetraethyl orthosilicate and phosphoric acid, after curing, creates a highly cross-linked and dense coating structure, further strengthening the physical barrier effect. This combination of multiple anti-corrosion mechanisms allows the coating to maintain excellent protective performance under corrosive environments such as salt spray and acid / alkali conditions, significantly extending the service life of steel structures, storage tanks, and other substrates, and reducing subsequent maintenance costs.

[0041] 3. This invention ensures the stability of the coating system and improves its applicability to various applications by modifying raw materials and optimizing the preparation process. At the raw material level, modified wollastonite and modified zinc phosphate enhance compatibility with the inorganic film-forming matrix, preventing component sedimentation or stratification. Fumed silica, acting as a thixotropic agent, regulates the rheological properties of the coating, prevents solid particle sedimentation during standing, and maintains good fluidity during stirring and application. In terms of the preparation process, the coating is prepared in two components, A and B, to avoid premature reaction leading to gelation. The sand mill uses segmented temperature control to protect active components such as zinc powder and silica-coated aluminum powder from high-temperature damage, while ensuring uniform particle size after grinding. Isopropanol is used to adjust the viscosity to 60-70 s, and phosphoric acid is used to adjust the pH to 4-5, making the coating suitable for various application methods such as spraying and brushing. The resulting coating is smooth and free of defects such as sagging and pinholes, improving application efficiency and coating appearance quality.

[0042] 4. While achieving high performance, the coating also meets environmental protection requirements and excellent mechanical properties, further expanding its application scenarios. In terms of raw material selection, no toxic or harmful organic additives are added. The main components are inorganic mineral fillers and inorganic film-forming agents, with low volatile organic compound content, meeting modern environmental standards. It can be used in food processing workshops, drinking water facilities, and other fields with high environmental requirements. Regarding mechanical properties, the flake-like silica-coated aluminum powder and modified wollastonite form a three-dimensional support structure in the coating, significantly improving the coating's adhesion, hardness, and wear resistance. The flake-like structure of the silica-coated aluminum powder enhances the bonding area between the coating and the substrate, while the fibrous structure of the modified wollastonite improves the coating's impact and scratch resistance, making it less prone to damage when subjected to external impacts and friction, maintaining its complete protective performance. This makes it suitable for scenarios requiring both protection and mechanical properties, such as bridge railings and machinery housings, further broadening the coating's application range. Detailed Implementation

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0044] Example 1: Preparation of anti-slip inorganic zinc coating. The specific preparation steps are as follows:

[0045] S1. Dry zinc powder, titanium dioxide, and mica powder at 100℃ for 2 hours; activate fumed silica at 120℃ for 1 hour.

[0046] S2. Add 18 parts of deionized water, 12 parts of isopropanol, and 3 parts of ethylene glycol to the dispersion vessel and stir at 500 r / min for 5 min. Then add 65 parts of zinc powder, 6 parts of titanium dioxide, 6 parts of mica powder, 4 parts of fumed silica, and 2 parts of silica-coated aluminum powder in sequence. Stir for 15 min after each addition of raw material. Finally, add 18 parts of zinc phosphate and 12 parts of wollastonite and stir for 30 min to prepare component A.

[0047] S3. Add 28 parts of tetraethyl orthosilicate to another reactor, stir at 300 r / min, slowly add 5 parts of phosphoric acid dropwise, and finish the addition in 20 min. Control the temperature at 25℃, continue stirring for 1 h, then add 4 parts of zinc nitrate and stir for 10 min to prepare component B.

[0048] Components S4 and B are added to component A at a rate of 1 mL / s and stirred at 600 r / min for 30 min to ensure uniform mixing. Then, the mixture is transferred to a sand mill, and 1 mm diameter zirconium beads are added at a mass ratio of 3:1 to the system. The mixture is then ground at 1500 r / min for 2 h. The temperature is controlled at 25℃ for the first 1 h and at 30℃ for the next 1-2 h. The particle size is controlled at 7-9 μm. The mixture is filtered using a filter bag with a pore size of 150 μm. After filtration, the viscosity is tested at 25℃ using a Forte 4 cup. The viscosity is adjusted to 60 s with isopropanol and the pH is adjusted to 4 with phosphoric acid to obtain the anti-slip inorganic zinc coating.

[0049] Example 2: Preparation of anti-slip inorganic zinc coating. The specific preparation steps are as follows:

[0050] S1. Dry zinc powder, titanium dioxide, and mica powder at 110℃ for 3 hours; activate fumed silica at 130℃ for 2 hours;

[0051] S2. Add 22 parts of deionized water, 16 parts of isopropanol, and 5 parts of ethylene glycol to the dispersion vessel and stir at 600 r / min for 10 min. Then add 75 parts of zinc powder, 10 parts of titanium dioxide, 8 parts of mica powder, 6 parts of fumed silica, and 4 parts of silica-coated aluminum powder in sequence. Stir for 20 min after each addition of raw material. Finally, add 22 parts of zinc phosphate and 18 parts of wollastonite and stir for 40 min to prepare component A.

[0052] S3. Add 32 parts of tetraethyl orthosilicate to another reactor, stir at 400 r / min, slowly add 7 parts of phosphoric acid dropwise over 30 min, keep the temperature at 30℃, continue stirring for 1.5 h, then add 5 parts of zinc nitrate and stir for 15 min to prepare component B.

[0053] S4 and B components were added to component A at a rate of 1 mL / s and stirred at 700 r / min for 35 min to ensure uniform mixing. Then, the mixture was transferred to a sand mill, and 1 mm diameter zirconium beads were added at a mass ratio of 3:1 to the system. The mixture was ground at 1800 r / min for 2.5 h. The temperature was controlled at 30 °C for the first 1 h and at 35 °C for the next 1-2.5 h. The particle size was controlled at 7-9 μm. The mixture was filtered through a filter bag with a pore size of 150 μm. After filtration, the viscosity was tested at 25 °C using a Forte 4 cup. The viscosity was adjusted to 70 s with isopropanol and the pH was adjusted to 5 with phosphoric acid to obtain the anti-slip inorganic zinc coating.

[0054] Example 3: Preparation of anti-slip inorganic zinc coating. The specific preparation steps are as follows:

[0055] S1. Dry zinc powder, titanium dioxide, and mica powder at 105℃ for 2.5h; activate fumed silica at 125℃ for 1.5h.

[0056] S2. Add 20 parts of deionized water, 14 parts of isopropanol, and 4 parts of ethylene glycol to the dispersion vessel and stir at 550 r / min for 8 min. Then add 70 parts of zinc powder, 8 parts of titanium dioxide, 7 parts of mica powder, 5 parts of fumed silica, and 3 parts of silica-coated aluminum powder in sequence. Stir for 18 min after each addition of raw material. Finally, add 20 parts of zinc phosphate and 15 parts of wollastonite and stir for 35 min to prepare component A.

[0057] S3. Add 30 parts of tetraethyl orthosilicate to another reactor, stir at 350 r / min, slowly add 6 parts of phosphoric acid dropwise over 25 min, keep the temperature at 27℃, continue stirring for 1.2 h, then add 4 parts of zinc nitrate and stir for 12 min to prepare component B.

[0058] S4 and B components were added to component A at a rate of 1 mL / s and stirred at 650 r / min for 32 min to ensure uniform mixing. Then, the mixture was transferred to a sand mill, and 1 mm diameter zirconium beads were added at a mass ratio of 3:1 to the system. The mixture was ground at 1650 r / min for 2.2 h. The temperature was controlled at 27℃ for the first hour and at 32℃ for the next 1-2.2 h. The particle size was controlled at 7-9 μm. The mixture was filtered through a filter bag with a pore size of 150 μm. After filtration, the viscosity was tested at 25℃ using a Forte 4 cup. The viscosity was adjusted to 65 s with isopropanol and the pH was adjusted to 4.5 with phosphoric acid to obtain the anti-slip inorganic zinc coating.

[0059] Example 4: Preparation of modified zinc phosphate. The specific preparation steps are as follows:

[0060] A1. Weigh 20g of zinc phosphate into a beaker, add 35mL of deionized water, and stir with a magnetic stirrer at 300r / min for 20min to form a uniform suspension; measure 7mL of silane coupling agent KH-560 and 2.5g of lignin, add 4mL of ethanol, and disperse with ultrasonication at 250W for 10min to prepare a modifier solution. Pour the modifier solution into the suspension and stir at 350r / min for 2.5h in a constant temperature water bath at 60℃. Then filter with a Buchner funnel, wash the filter cake three times with a 1:1 volume ratio ethanol-water mixture, and finally vacuum dry at 75℃ for 4h to obtain the first modified zinc phosphate.

[0061] A2. Take 20g of the first modified zinc phosphate, add 50mL of anhydrous ethanol, and disperse it in a three-necked flask using ultrasonication at 300W for 20min to form a stable dispersion. Add 11mL of tetraethyl orthosilicate at a rate of 1 drop / second, and simultaneously add 1mol / L hydrochloric acid to adjust the pH to 3. Keep stirring at 300r / min, reflux at 68℃ for 3h, cool and centrifuge for 15min, wash the precipitate three times with anhydrous ethanol, dry it at 105℃ for 3.5h and pass it through a 200-mesh sieve to obtain the second modified zinc phosphate.

[0062] A3. Weigh 20g of the second modified zinc phosphate, add 25mL of deionized water and stir to form a suspension. Add 3.5g of lanthanum nitrate and stir until completely dissolved. Add 10% ammonia water to adjust the pH to 8.5. Heat to 80℃ and keep the temperature for 2h. After filtration, wash the filter cake with deionized water until neutral. Place it in a muffle furnace and calcine at 380℃ for 1.2h at a rate of 4℃ / min. After natural cooling, the modified zinc phosphate is obtained.

[0063] Example 5: Preparation of modified zinc phosphate. The specific preparation steps are as follows:

[0064] A1. Weigh 20g of zinc phosphate into a beaker, add 45mL of deionized water, and stir with a magnetic stirrer at 350r / min for 30min to form a uniform suspension; measure 9mL of silane coupling agent KH-560 and 3.5g of lignin, add 6mL of ethanol, and disperse with ultrasonication at 250W for 20min to prepare a modifier solution. Pour the modifier solution into the suspension and stir at 400r / min for 3.5h in a constant temperature water bath at 70℃. Then filter with a Buchner funnel, wash the filter cake 4 times with a 1:1 volume ratio ethanol-water mixture, and finally vacuum dry at 85℃ for 5h to obtain the first modified zinc phosphate.

[0065] A2. Take 20g of the first modified zinc phosphate, add 60mL of anhydrous ethanol, and sonicate in a three-necked flask at 300W for 25min to form a stable dispersion. Add 13mL of tetraethyl orthosilicate at a rate of 1 drop / second, and simultaneously add 1mol / L hydrochloric acid to adjust the pH to 4. Keep stirring at 300r / min and reflux at 72℃ for 4h. After cooling, centrifuge for 15min, wash the precipitate 4 times with anhydrous ethanol, dry it at 115℃ for 4.5h, and pass it through a 200-mesh sieve to obtain the second modified zinc phosphate.

[0066] A3. Weigh 20g of the second modified zinc phosphate, add 35mL of deionized water and stir to form a suspension. Add 4.5g of lanthanum nitrate and stir until completely dissolved. Add 10% ammonia water to adjust the pH to 9.5. Heat to 90℃ and keep the temperature for 3h. After filtration, wash the filter cake with deionized water until neutral. Place it in a muffle furnace and calcine at 420℃ for 1.8h at a rate of 6℃ / min. After natural cooling, the modified zinc phosphate is obtained.

[0067] Example 6: Preparation of modified wollastonite. The specific preparation steps are as follows:

[0068] B1. Weigh 15g of wollastonite and put it into a beaker. Add 135mL of a mixture of 10% hydrochloric acid and 35mL of 5% citric acid. Stir the mixture at 300r / min for 4.5h in a constant temperature water bath at 78℃. After filtration, wash the filter cake with deionized water until pH=7. Dry it under vacuum at 70℃ for 4.5h to obtain the first modified wollastonite.

[0069] B2. Take 15g of the first modified wollastonite, add 110mL of deionized water and ultrasonically disperse for 20min at 300W power. Transfer to a four-necked flask, add 3mL of styrene, 2mL of butyl acrylate and 0.7g of ammonium persulfate. Stir and react at 300r / min at 73℃ for 3.5h under nitrogen protection. After cooling, centrifuge for 15min. Wash the precipitate twice with deionized water, dry at 95℃ for 4h and pass through a 300-mesh sieve to obtain the second modified wollastonite.

[0070] B3. Take 15g of the second modified wollastonite, add 75mL of deionized water and stir to form a suspension. Add 18mL of 0.8mol / L barium chloride solution and stir for 8min. Add 17mL of 0.8mol / L sodium sulfate solution in 14min. Stir at 250r / min at 28℃ for 1.8h. After the reaction, filter and wash the filter cake with deionized water until no chloride ions are detected in the filtrate. Finally, dry in a forced-air dryer at 85℃ for 3.5h to obtain the modified wollastonite.

[0071] Example 7: Preparation of modified wollastonite. The specific preparation steps are as follows:

[0072] B1. Weigh 15g of wollastonite into a beaker, add 145mL of a mixture of 10% hydrochloric acid and 45mL of 5% citric acid, and stir the mixture at 350r / min for 5.5h in a constant temperature water bath at 82℃. After filtration, wash the filter cake with deionized water until pH=7, and dry it under vacuum at 80℃ for 5.5h to obtain the first modified wollastonite.

[0073] B2. Take 15g of the first modified wollastonite, add 130mL of deionized water and ultrasonically disperse for 30min at 300W power. Transfer to a four-necked flask, add 4mL of styrene, 3mL of butyl acrylate and 0.9g of ammonium persulfate. Stir and react at 77℃ and 350r / min for 4.5h under nitrogen protection. After cooling, centrifuge for 15min. Wash the precipitate three times with deionized water, dry at 105℃ for 5h and pass through a 300-mesh sieve to obtain the second modified wollastonite.

[0074] B3. Take 15g of the second modified wollastonite, add 85mL of deionized water and stir to form a suspension. Add 22mL of 0.8mol / L barium chloride solution and stir for 12min. Add 19mL of 0.8mol / L sodium sulfate solution in 16min. Stir at 300r / min at 32℃ for 2.2h. After the reaction, filter and wash the filter cake with deionized water until no chloride ions are detected in the filtrate. Finally, dry at 95℃ for 4.5h to obtain the modified wollastonite.

[0075] Comparative Example 1: An anti-slip inorganic zinc coating was prepared. The specific preparation steps are as follows:

[0076] The remaining steps remain unchanged, except that the zinc phosphate in Example 3 is replaced with the modified zinc phosphate prepared in Example 4 to prepare an anti-slip inorganic zinc coating.

[0077] Comparative Example 2: Preparation of anti-slip inorganic zinc coating. The specific preparation steps are as follows:

[0078] The remaining steps remain unchanged, except that the wollastonite in Example 3 is replaced with the modified wollastonite prepared in Example 7 to prepare the anti-slip inorganic zinc coating.

[0079] Comparative Example 3: An anti-slip inorganic zinc coating was prepared. The specific preparation steps are as follows:

[0080] The remaining steps remain unchanged, except that the zinc phosphate in Example 3 is replaced with the modified zinc phosphate prepared in Example 4, and the wollastonite is replaced with the modified wollastonite prepared in Example 7, to prepare an anti-slip inorganic zinc coating.

[0081] Performance testing

[0082] Test Project Test Standards Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Anti-slip performance (coefficient of friction) GB / T9263-2020 Dry: 0.58 Moist: 0.42 Oil: 0.35 Dry: 0.61 Moist: 0.45 Oil: 0.38 Dry: 0.65 Moist: 0.48 Oil: 0.41 Dry: 0.72 Moist: 0.55 Oil: 0.48 Dry: 0.78 Moist: 0.62 Oil: 0.55 Dry: 0.85 Moist: 0.70 Oil: 0.63 Corrosion resistance (1000h neutral salt spray test) GB / T1771-2007 Localized pitting corrosion, covering 8.5% of the area; adhesion level 4. Minor pitting corrosion, covering 6.2% of the area; adhesion level 3. Minor corrosion at the edges, covering an area of ​​3.8%; adhesion level 2. No obvious rust, slight localized loss of gloss; adhesion grade 1. No rust, slight localized loss of gloss; adhesion grade 1. No rust, good gloss; adhesion grade 1 hardness GB / T6739-2022 HB grade H-class 2H level 3H level 4H level 5H level Impact resistance GB / T1732-2020 20kg·cm 25kg·cm 30kg·cm 38kg·cm 45kg·cm 55kg·cm Room temperature sedimentation rate HG / T4759-2014 After standing at room temperature for 30 days: 12.5% After standing at room temperature for 30 days: 9.8% After standing at room temperature for 30 days: 6.3% After standing at room temperature for 30 days: 3.1% After standing at room temperature for 30 days: 2.5% After standing at room temperature for 60 days: 0.8% Low temperature stability HG / T4759-2014 After standing at -5℃ for 7 days: slight stratification After standing at -5℃ for 7 days: no obvious stratification. After standing at -5℃ for 7 days: no stratification. After standing at -5℃ for 15 days: no stratification. After standing at -5℃ for 15 days: no stratification. After standing at -5℃ for 30 days: no stratification.

[0083] According to performance test data, the performance of this anti-slip inorganic zinc coating shows a significant improvement trend with raw material modification and formulation optimization: In terms of anti-slip performance, Examples 1-3 without modified raw materials have lower coefficients of friction, while Comparative Example 1 using modified zinc phosphate, Comparative Example 2 using modified wollastonite, and Comparative Example 3 using both have significantly higher coefficients of friction. Comparative Example 3 reaches 0.85, 0.70, and 0.63 in dry, humid, and oily environments, respectively. In terms of corrosion resistance, Examples 1-3 showed varying degrees of rust after 1000 hours of neutral salt spray testing (rust area 3.8%-8.5%, adhesion 2...). Examples 1-3 showed no rust or only slight loss of gloss, and all achieved Grade 1 adhesion. In terms of hardness and impact strength, Examples 1-3 were HB-2H grade and 20-30 kg·cm, respectively, while Comparative Examples 1-3 were improved to 3H-5H grade and 38-55 kg·cm. In terms of stability, Examples 1-3 had a settling rate of 6.3%-12.5% ​​at room temperature for 30 days and partial stratification after standing at -5℃ for 7 days, while Comparative Example 3 had a settling rate of only 0.8% at room temperature for 60 days and no stratification after standing at -5℃ for 30 days. Overall, the modification of raw materials can significantly improve the anti-slip, anti-corrosion, mechanical and stability properties of the coating.

[0084] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. An anti-slip inorganic zinc coating, characterized in that: It contains the following raw materials in parts by weight: 65-75 parts zinc powder, 6-10 parts titanium dioxide, 6-8 parts mica powder, 18-22 parts deionized water, 15-20 parts isopropanol, 3-5 parts ethylene glycol, 12-18 parts modified wollastonite, 4-6 parts fumed silica, 2-4 parts silica-coated aluminum powder, 18-22 parts modified zinc phosphate, 28-32 parts tetraethyl orthosilicate, 5-7 parts phosphoric acid, and 4-6 parts zinc nitrate. The modified zinc phosphate is prepared using the following specific steps: A1. Weigh zinc phosphate and place it in a beaker. Add deionized water and stir with a magnetic stirrer at 300-350 r / min for 20-30 min to form a uniform suspension. Measure silane coupling agent KH-560 and lignin, add ethanol, and disperse with ultrasonication at 250 W for 10-20 min to prepare a modifier solution. Pour the modifier solution into the suspension and stir at 350-400 r / min for 2.5-3.5 h in a constant temperature water bath at 60-70℃. Then filter with a Buchner funnel. Wash the filter cake 3-4 times with a 1:1 volume ratio ethanol-water mixture. Finally, vacuum dry at 75-85℃ for 4-5 h to obtain the first modified zinc phosphate. A2. Take the first modified zinc phosphate, add anhydrous ethanol, and ultrasonically disperse it in a three-necked flask at 300W for 20-25 min to form a stable dispersion. Add tetraethyl orthosilicate dropwise at a rate of 1 drop / second, and simultaneously add 1 mol / L hydrochloric acid to adjust the pH to 3-4. Keep stirring at 300 r / min and reflux at 68-72℃ for 3-4 h. After cooling, centrifuge for 15 min. Wash the precipitate 3-4 times with anhydrous ethanol, dry it in a forced-air dryer at 105-115℃ for 3.5-4.5 h, and then pass it through a 200 mesh sieve to obtain the second modified zinc phosphate. A3. Weigh the second batch of modified zinc phosphate, add deionized water and stir to form a suspension. Add lanthanum nitrate and stir until completely dissolved. Add 10% ammonia water by mass to adjust the pH to 8.5-9.

5. Heat to 80-90℃ and keep the temperature for 2-3 hours. After filtration, wash the filter cake with deionized water until neutral. Place it in a muffle furnace and heat to 380-420℃ at a rate of 4-6℃ / min for calcination for 1.2-1.8 hours. After natural cooling, the modified zinc phosphate is obtained. The modified wollastonite is prepared using the following specific steps: B1. Weigh wollastonite and place it in a beaker. Add a mixed acid consisting of hydrochloric acid and citric acid. Stir the mixture at 300-350 r / min for 4.5-5.5 h in a constant temperature water bath at 78-82℃. After filtration, wash the filter cake with deionized water until pH=7. Dry it under vacuum at 70-80℃ for 4.5-5.5 h to obtain the first modified wollastonite. B2. Take the first modified wollastonite, add deionized water and ultrasonically disperse it for 20-30 min at 300W power. Transfer it to a four-necked flask, add styrene, butyl acrylate and ammonium persulfate, and stir the mixture at 300-350 r / min at 73-77℃ for 3.5-4.5 h under nitrogen protection. After cooling, centrifuge for 15 min, wash the precipitate 2-3 times with deionized water, dry it at 95-105℃ for 4-5 h, and then pass it through a 300-mesh sieve to obtain the second modified wollastonite. B3. Take the second modified wollastonite, add deionized water and stir to form a suspension. Add 0.8 mol / L barium chloride solution dropwise and stir for 8-12 min. Add 0.8 mol / L sodium sulfate solution dropwise over 14-16 min. Stir at 250-300 r / min at 28-32℃ for 1.8-2.2 h. After the reaction, filter the mixture. Wash the filter cake with deionized water until no chloride ions are detected in the filtrate. Finally, dry the mixture in a forced-air dryer at 85-95℃ for 3.5-4.5 h to obtain the modified wollastonite.

2. The anti-slip inorganic zinc coating according to claim 1, characterized in that: The zinc powder has a particle size of 10-20 μm and undergoes surface degreasing treatment. The specific steps of the degreasing treatment are as follows: add the zinc powder to an 8% sodium hydroxide solution, stir at 250 r / min for 20 min at 45℃, then wash with deionized water until neutral, and dry in a forced-air dryer at 95℃ for 3 h.

3. The anti-slip inorganic zinc coating according to claim 1, characterized in that: The silica-coated aluminum powder is in the form of flake aluminum powder with a diameter-to-thickness ratio of 50-80:1, and its surface is coated with a 2% by mass silica protective film. The protective film is prepared as follows: 100g of aluminum powder is dispersed in 500mL of a 3:1 volume ratio ethanol-water mixed solution, 0.5g of silane coupling agent KH-550 is added, and the mixture is stirred at 30℃ for 30min. Then, a mixture of 6g of tetraethyl orthosilicate and 1.2mL of hydrochloric acid with a pH of 4.5 is added dropwise. The temperature is controlled at 50℃ and the reaction is carried out at 300r / min for 2h. The temperature is then raised to 80℃ and the reaction is carried out for 1h. After centrifugation and washing, the mixture is vacuum dried at 60℃ for 2h.

4. The anti-slip inorganic zinc coating according to claim 1, characterized in that: The ratio of zinc phosphate to deionized water in the suspension of A1 is 20g:35-45mL; the ratio of silane coupling agent KH-560, lignin, and ethanol in the modifier solution is 7-9mL:2.5-3.5g:4-6mL. The ratio of the first modified zinc phosphate, anhydrous ethanol, and tetraethyl orthosilicate in A2 is 20g: 50-60mL: 11-13mL; The ratio of the second modified zinc phosphate, deionized water, and lanthanum nitrate in A3 is 20g: 25-35mL: 3.5-4.5g.

5. The anti-slip inorganic zinc coating according to claim 1, characterized in that: The ratio of wollastonite to mixed acid in B1 is 15g:170-190mL; wherein the mixed acid is prepared by 135-145mL of 10% hydrochloric acid and 35-45mL of 5% citric acid. The ratio of the first modified wollastonite, deionized water, styrene, butyl acrylate, and ammonium persulfate in B2 is 15g: 110-130mL: 3-4mL: 2-3mL: 0.7-0.9g; The ratio of the amount of the second modified wollastonite, deionized water, barium chloride solution, and sodium sulfate solution in B3 is 15g:75-85mL:18-22mL:17-19mL.

6. The method for preparing an anti-slip inorganic zinc coating according to claim 1, characterized in that: Specifically, it includes the following steps: S1. Dry zinc powder, titanium dioxide, and mica powder at 100-110℃ for 2-3 hours; activate fumed silica at 120-130℃ for 1-2 hours. S2. Add 18-22 parts of deionized water, 12-16 parts of isopropanol, and 3-5 parts of ethylene glycol to the dispersion vessel, and stir at 500-600 r / min for 5-10 min. Then add 65-75 parts of zinc powder, 6-10 parts of titanium dioxide, 6-8 parts of mica powder, 4-6 parts of fumed silica, and 2-4 parts of silica-coated aluminum powder in sequence, stirring for 15-20 min after each addition of raw material. Finally, add 18-22 parts of modified zinc phosphate and 12-18 parts of modified wollastonite, and stir for 30-40 min to prepare component A. S3. Add 28-32 parts of tetraethyl orthosilicate to another reactor, stir at 300-400 r / min, slowly add 5-7 parts of phosphoric acid dropwise over 20-30 min, keep the temperature at 25-30℃, continue stirring for 1-1.5 h, then add 4-5 parts of zinc nitrate, stir for 10-15 min to prepare component B. S4 and B components are added to component A at a rate of 1 mL / s, and stirred at 600-700 r / min for 30-35 min to ensure uniform mixing; Then transfer the mixture to a sand mill, add zirconium beads with a diameter of 1 mm at a mass ratio of 3:1, and grind at 1500-1800 r / min for 2-2.5 h, controlling the particle size to 7-9 μm. Filter the mixture using a filter bag with a pore size of 150 μm. After filtration, test the viscosity at 25℃ using a Forte 4 cup, adjust the viscosity to 60-70 s with isopropanol, and adjust the pH to 4-5 with phosphoric acid to obtain the anti-slip inorganic zinc coating.

7. The method for preparing an anti-slip inorganic zinc coating according to claim 6, characterized in that: During the grinding process of the sand mill, a segmented temperature control method is adopted. The temperature is controlled at 25-30℃ in the first hour and then at 30-35℃ in the subsequent hours.