Antiskid inorganic zinc coating and preparation method thereof

Abstract

The invention discloses an antiskid inorganic zinc coating and a preparation method thereof, and relates to the technical field of functional protective coatings. The anti-skid inorganic zinc coating is prepared from the following raw materials in parts by weight: 65 to 75 parts of zinc powder, 6 to 10 parts of titanium dioxide, 6 to 8 parts of mica powder, 18 to 22 parts of deionized water, 15 to 20 parts of isopropanol, 3 to 5 parts of ethylene glycol, 12 to 18 parts of modified wollastonite, 4 to 6 parts of fumed silica, 2 to 4 parts of silicon dioxide coated aluminum powder, 18 to 22 parts of modified zinc phosphate, 28 to 32 parts of tetraethoxysilane, 5 to 7 parts of phosphoric acid and 4 to 6 parts of zinc nitrate. The anti-skid inorganic zinc coating and the preparation method have remarkable advantages. The raw material ratio is scientific, the zinc powder is degreased, and the aluminum powder is coated, so that the performance is improved; the preparation process of modified zinc phosphate and modified wollastonite is fine, and the stability of the coating is enhanced. Temperature and speed are controlled in stages during preparation, grinding and filtering links are strict, and uniform particle size and adaptive viscosity of the coating are guaranteed. And finally, the paint has outstanding skid resistance and corrosion resistance and strong applicability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional protective coatings, in particular to an anti-skid inorganic zinc coating and a preparation method thereof. BACKGROUND

[0002] In the field of industrial corrosion protection and functional protection, inorganic zinc coatings are widely used in bridge, marine engineering, oil storage tank, steel structure and other scenes due to their excellent corrosion resistance, high temperature resistance and environmental protection characteristics. However, traditional inorganic zinc coatings still have many technical problems in practical application, and it is difficult to meet the anti-skid and long-term protection requirements under complex working conditions.

[0003] On the one hand, the anti-skid performance of traditional inorganic zinc coatings depends on single aggregate addition, such as ordinary quartz sand and talc powder. Such aggregates have poor compatibility with the coating matrix, are prone to sedimentation and agglomeration, resulting in uneven roughness of the coating surface, unstable anti-skid effect, and a significant decrease in friction coefficient in humid and oily environments, which can easily cause safety accidents such as slipping and equipment sliding.

[0004] On the other hand, the corrosion resistance of traditional products is significantly affected by the characteristics of raw materials. Unmodified zinc powder has poor adhesion with film-forming materials due to surface oil and oxidation layer, and the coating is prone to pinholes and cracking. Corrosion inhibitors such as zinc phosphate have poor dispersibility and cannot uniformly play a corrosion inhibition role, resulting in a shortened protective life of the coating in salt spray, acid and alkali environments, and the need for frequent recoating, which increases maintenance costs.

[0005] At the same time, traditional preparation processes have defects. For example, improper temperature control during the grinding process can damage the activity of raw materials, uneven dispersion of materials during the mixing stage can cause fluctuations in coating performance, and the viscosity and particle size of the final product are difficult to adapt to different construction methods such as spraying and brushing, which affects construction efficiency and coating quality. In addition, some coatings add toxic additives to improve performance, which does not meet modern environmental protection requirements and limits their application in food processing, drinking water facilities and other fields.

[0006] Therefore, it is a key requirement to develop an inorganic zinc coating with reasonable raw material modification, precise preparation process, stable anti-skid performance and long-term corrosion resistance, and environmental protection standards. SUMMARY

[0007] In view of the deficiencies of the prior art, the present application provides an anti-skid inorganic zinc coating and a preparation method, which solves the problems of unstable anti-skid performance, short corrosion life, system sedimentation and insufficient environmental protection of traditional inorganic zinc coatings.

[0008] To achieve the above purpose, the present application is realized by the following technical solutions:

[0009] The anti-skid inorganic zinc coating comprises the following raw materials in parts by weight: 65-75 parts of zinc powder, 6-10 parts of titanium white powder, 6-8 parts of mica powder, 18-22 parts of deionized water, 15-20 parts of isopropyl alcohol, 3-5 parts of ethylene glycol, 12-18 parts of modified wollastonite, 4-6 parts of fumed silica, 2-4 parts of aluminum powder coated with silicon dioxide, 18-22 parts of modified zinc phosphate, 28-32 parts of ethyl silicate, 5-7 parts of phosphoric acid, and 4-6 parts of zinc nitrate.

[0010] Further, the particle size of the zinc powder is 10-20 mu m, and the zinc powder is subjected to surface degreasing treatment, and the specific steps of the degreasing treatment are as follows: the zinc powder is added into a sodium hydroxide solution with a mass fraction of 8%, and stirred at 45 DEG C and 250 r / min for 20 min, so that the oil stains and oxide layers on the surface of the zinc powder can be completely removed, and the influence of the oil stains on the binding force between the zinc powder and the film-forming material is avoided; then the zinc powder is washed with deionized water until neutral, and air-dried at 95 DEG C for 3 h, so that the residual alkali liquid can be prevented from damaging the stability of the coating system, and the electrochemical activity of the zinc powder is finally improved, so that the zinc powder can more efficiently play a sacrificial anode anticorrosion role.

[0011] Further, the aluminum powder coated with silicon dioxide is flaky aluminum powder, the diameter-thickness ratio of which is 50-80:1, and the surface of the aluminum powder is coated with a silicon dioxide protective film with a mass fraction of 2%, which can isolate the aluminum powder from air and moisture, and prevent the aluminum powder from being oxidized and losing effectiveness; at the same time, the flaky structure cooperates with the protective film to construct a three-dimensional support structure in the coating, so as to enhance the surface friction coefficient and mechanical strength of the coating; and the protective film is prepared in the following manner: 100 g of aluminum powder is dispersed in 500 mL of an ethanol-water mixed solution with a volume ratio of 3:1, 0.5 g of silane coupling agent KH-550 is added, stirring is carried out at 30 DEG C for 30 min, a mixed solution of 6 g of ethyl silicate and 1.2 mL of hydrochloric acid with a pH of 4.5 is added dropwise, the temperature is controlled at 50 DEG C, and reaction is carried out at 300 r / min for 2 h, and then the temperature is increased to 80 DEG C, and reaction is carried out for 1 h, after centrifugal washing, vacuum drying is carried out at 60 DEG C for 2 h.

[0012] Further, the modified zinc phosphate is prepared in the following specific steps:

[0013] A1, take the zinc phosphate into a beaker, add deionized water, 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 prepare a modifier solution by ultrasonic dispersion at 250 W for 10-20 min; pour the modifier solution into the suspension, stir at 350-400 r / min in a constant temperature water bath at 60-70℃ for 2.5-3.5 h, which can improve the compatibility of zinc phosphate with the coating matrix and avoid zinc phosphate agglomeration; constant temperature water bath reaction can promote the full combination of the modifier and the surface of zinc phosphate, and preliminarily improve its dispersibility; then use a Buchner funnel to filter, wash the filter cake with a volume ratio of 1:1 ethanol-water mixture for 3-4 times, and finally vacuum dry at 75-85℃ for 4-5 h to obtain the first modified zinc phosphate;

[0014] A2, take the first modified zinc phosphate, add anhydrous ethanol, and use a three-necked flask to ultrasonically disperse at 300 W for 20-25 min to form a stable dispersion liquid; add tetraethyl orthosilicate at a rate of 1 drop per second, which can form a dense siloxane coating layer on the surface of zinc phosphate to enhance the acid and alkali resistance of zinc phosphate; 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 with anhydrous ethanol for 3-4 times, dry at 105-115℃ with a blast for 3.5-4.5 h, and then pass through a 200 mesh sieve to obtain the second modified zinc phosphate; sieving controls the uniform particle size of the modified zinc phosphate, avoiding performance fluctuations of the coating caused by particle size differences;

[0015] A3, take the second modified zinc phosphate, add deionized water to form a suspension, add lanthanum nitrate and stir until it is completely dissolved, add 10% ammonia water by mass fraction to adjust the pH to 8.5-9.5, heat to 80-90℃ and keep for 2-3 h, wash the filter cake with deionized water until it is neutral, put it into a muffle furnace, heat at a rate of 4-6℃ / min to 380-420℃ and calcine for 1.2-1.8 h, and then naturally cool to obtain the modified zinc phosphate. Lanthanum nitrate can form a composite corrosion inhibitor with zinc phosphate to improve the corrosion inhibition efficiency; gradient heating can avoid structure cracking of zinc phosphate due to sudden temperature rise, and finally make the modified zinc phosphate uniformly dispersed and form a dense passivation film to block the penetration of corrosion ions.

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

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

[0018] Further, the second modification of the A3 zinc phosphate, deionized water, lanthanum nitrate is 20g: 25-35mL: 3.5-4.5g.

[0019] The silane coupling agent KH-560 in A1 contains an epoxy group, which can react with the hydroxyl group on the surface of zinc phosphate to form a chemical bond. Lignin is attached to the surface of zinc phosphate through adsorption, which improves the compatibility of zinc phosphate and the coating matrix, avoids agglomeration, and lays the foundation for subsequent modification.

[0020] In A2, tetraethyl orthosilicate is hydrolyzed under acidic conditions to form siloxane, which uniformly coats the surface of zinc phosphate to form a dense layer, enhancing its acid and alkali resistance, and further optimizing the dispersibility to ensure uniform distribution in the coating.

[0021] In A3, lanthanum nitrate reacts with zinc phosphate to form a composite corrosion inhibitor component, which is fixed by gradient temperature calcination to avoid cracking of the zinc phosphate structure, ultimately improving the corrosion inhibition efficiency, and can react with the metal substrate to form a dense passivation film to block corrosion ions.

[0022] Further, the modified wollastonite is prepared according to the following steps:

[0023] In B1, wollastonite is weighed and placed in a beaker, mixed acid composed of hydrochloric acid and citric acid is added, and stirring is carried out at 300-350r / min under constant temperature water bath at 78-82℃ for 4.5-5.5h. After filtration, the filter cake is washed with deionized water until pH=7, and vacuum dried at 70-80℃ for 4.5-5.5h to obtain the first modified wollastonite. The mixed acid can etch the surface of wollastonite to form a rough and porous structure, increasing the contact area with the coating matrix and laying the foundation for subsequent modification. Washing to neutral and vacuum drying can remove residual acid to prevent abnormal pH of the coating;

[0024] In B2, the first modified wollastonite is taken and dispersed with 300W ultrasonic power for 20-30min with deionized water, then transferred to a four-necked flask, styrene, butyl acrylate and ammonium persulfate are added, and stirring is carried out at 300-350r / min under nitrogen protection at 73-77℃ for 3.5-4.5h to avoid oxidation of monomers and ensure stable grafting reaction. After cooling, centrifugation is carried out for 15min, the precipitate is washed with deionized water for 2-3 times, dried at 95-105℃ for 4-5h, and then sieved through a 300 mesh sieve to obtain the second modified wollastonite. Ultrasonic dispersion can make the grafted polymer uniformly adhere to the surface of wollastonite, further improve the compatibility of wollastonite and inorganic film-forming system, and reduce sedimentation.

[0025] B3, taking the second modified wollastonite, adding deionized water to form a suspension, adding 0.8 mol / L barium chloride solution dropwise and stirring for 8-12 min, adding 0.8 mol / L sodium sulfate solution dropwise at 14-16 min, stirring at 28-32℃ and 250-300 r / min for 1.8-2.2 h, filtering after reaction, washing the filter cake with deionized water until no chloride ions are detected in the filtrate, and finally drying at 85-95℃ for 3.5-4.5 h to obtain modified wollastonite. By adding barium chloride and sodium sulfate dropwise, barium sulfate microparticles can be formed on the surface of wollastonite, increasing the surface roughness of wollastonite, and cooperating with its fibrous structure to build "micro-protrusion" anti-slip units on the surface of the coating, significantly improving the anti-slip performance.

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

[0027] Further, the amount 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] Further, the amount ratio 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 mixing 10% hydrochloric acid and 5% citric acid in B1 can selectively dissolve the impurities and part of the 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 the protection of nitrogen, ammonium persulfate initiates the polymerization reaction of styrene and butyl acrylate on the surface of wollastonite, forming an organic grafting layer, which greatly improves the compatibility of wollastonite and inorganic film-forming system and reduces the settlement during storage.

[0031] In B3, barium chloride and sodium sulfate react on the surface of wollastonite to form barium sulfate microparticles, which uniformly coat the surface of wollastonite, increase the surface roughness, cooperate with the fibrous structure, and build "micro-protrusion" anti-slip units on the surface of the coating, significantly enhancing the anti-slip performance.

[0032] A preparation method of an anti-slip inorganic zinc coating, specifically comprising the following steps:

[0033] S1, dry the zinc powder, titanium white powder and mica powder at 100-110 DEG C for 2-3h; activate the fumed silica at 120-130 DEG C for 1-2h to enhance its thixotropy, and prevent the 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 into a dispersion kettle, stir at 500-600 r / min for 5-10 min, then sequentially add 65-75 parts of zinc powder, 6-10 parts of titanium white powder, 6-8 parts of mica powder, 4-6 parts of fumed silica, and 2-4 parts of silica-coated aluminum powder, stir for 15-20 min after each addition to ensure uniform dispersion of each material and avoid excessive local concentration; 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 into another reaction kettle, stir at 300-400 r / min, slowly drop 5-7 parts of phosphoric acid, drop for 20-30 min, control the temperature at 25-30 DEG C, continue to stir for 1-1.5h, then add 4-5 parts of zinc nitrate, and stir for 10-15 min to prepare component B;

[0036] S4, add component B into component A at a rate of 1mL / s, stir at 600-700 r / min for 30-35 min to ensure uniform mixing; then transfer into a sand mill, add zirconium beads with a diameter of 1mm, and grind at 1500-1800 r / min for 2-2.5h with a mass ratio of 3:1 to control the particle size at 7-9um, filter with a filter bag with a pore size of 150um to ensure uniform particle size of the coating, adapt to spraying, brushing and other construction methods, and prevent fluctuations in the slip resistance and corrosion resistance of the coating due to uneven particle size; after filtration, detect the viscosity at 25 DEG C with a coating-4 cup, adjust to 60-70s with isopropanol, and adjust the pH to 4-5 with phosphoric acid to obtain the slip-resistant inorganic zinc coating.

[0037] Further, in the sand mill grinding process, the temperature is controlled in a segmented manner, the temperature is controlled at 25-30 DEG C in the initial 1h, and the temperature is controlled at 30-35 DEG C in the subsequent period, which can protect the initial performance of the material, improve the grinding efficiency and particle size uniformity in the later period, and finally ensure the stability and core properties such as slip resistance and corrosion resistance of the coating system.

[0038] The application provides a slip-resistant inorganic zinc coating and a preparation method.

[0039] 1、The present application is endowed with excellent and lasting anti-skid ability of the coating through multi-component synergistic optimization and structural design. From the selection of raw materials, the modified wollastonite is treated by mixed acid etching, organic monomer grafting and barium sulfate coating, and a rough and porous composite structure is formed on the surface, which not only improves the bonding strength with the coating matrix, but also can build uniform distribution of "micro-protrusion" anti-skid unit on the surface of the coating; at the same time, the flaky silica-coated aluminum powder and fumed silica are dispersed synergistically, and a three-dimensional interlaced support structure is formed inside the coating, which further enhances the surface friction coefficient. Compared with the traditional coating which relies on a single aggregate and is prone to sedimentation and anti-skid effect fluctuation, the combination of modified wollastonite, silica-coated aluminum powder and fumed silica in the present application can avoid aggregate agglomeration or falling off, and still maintain stable anti-skid performance even in harsh environments such as humidity and oil, effectively reducing the safety risks of personnel slipping and equipment slipping, and adapting to scenes such as bridges, offshore platforms and industrial workshop floors which have strict requirements for anti-skid.

[0040] 2、The coating system is synergistically combined by multiple corrosion protection mechanisms to build a long-acting protective barrier. The core corrosion protection component zinc powder is treated by surface degreasing to remove surface grease and oxide layer, improve its dispersibility and electrochemical activity in the coating, and more efficiently play the role of sacrificial anode protection; modified zinc phosphate not only has significantly improved dispersibility and can be uniformly distributed in the coating, but also can react with the surface of the metal substrate to form a dense phosphate passivation film, blocking the penetration of water, oxygen and corrosive ions; at the same time, the inorganic film-forming system formed by tetraethyl orthosilicate and phosphoric acid forms a coating structure with high cross-linking degree and good compactness after curing, further enhancing the physical barrier effect. The combination of multiple corrosion protection mechanisms enables the coating to maintain excellent protective performance in salt spray, acid and alkali corrosion environments, greatly prolonging the service life of steel structures, storage tanks and other substrates, and reducing the maintenance cost.

[0041] 3、The present application guarantees the stability of the coating system from the aspects of raw material modification and preparation process, and at the same time improves the construction adaptability. On the raw material level, modified wollastonite and modified zinc phosphate both improve the compatibility with the inorganic film-forming matrix, avoiding component sedimentation or stratification; fumed silica as a thixotropic agent can adjust the rheological properties of the coating, preventing solid particles from settling when standing, and maintaining good fluidity when stirring and construction. On the preparation process, A and B components are prepared separately to avoid premature reaction leading to coating gel; the grinding of sand mill adopts segmented temperature control, which not only protects the active components such as zinc powder and silica-coated aluminum powder from being damaged by high temperature, but also ensures uniform particle size of the coating after grinding, and then adjusts the viscosity to 60-70s by isopropyl alcohol and the pH to 4-5 by phosphoric acid, so that the coating is suitable for various construction methods such as spraying and brushing, and the coating after construction is smooth and flat without defects such as sagging and pinholes, improving the construction 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] S4, the B component is added to the A component at a rate of 1 mL / s, stirred at 600 r / min for 30 min to ensure uniform mixing; then transferred into a sand mill, 1 mm diameter zirconium beads are added, the mass ratio of the system is 3:1, and grinding is carried out at 1500 r / min for 2 h, the temperature is controlled at 25°C in the initial 1 h, and the temperature is controlled at 30°C in the subsequent 1-2 h, the particle size is controlled at 7-9 μm, and a filter bag with a pore size of 150 μm is used for filtration, after filtration, the viscosity is detected at 25°C with a ZO-4 cup, isopropanol is used to adjust to 60 s, and phosphoric acid is used to adjust the pH to 4, to obtain the anti-skid inorganic zinc coating.

[0049] Example 2, preparation of anti-skid inorganic zinc coating, the specific preparation steps are as follows:

[0050] S1, dry the zinc powder, titanium dioxide, and mica powder at 110°C for 3h; activate the fumed silica at 130°C for 2h;

[0051] S2, add 22 parts of deionized water, 16 parts of isopropanol, and 5 parts of ethylene glycol to a dispersion kettle, 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, finally add 22 parts of zinc phosphate and 18 parts of wollastonite, and stir for 40 min to prepare the A component;

[0052] S3, add 32 parts of tetraethyl orthosilicate to another reaction kettle, stir at 400 r / min, slowly add 7 parts of phosphoric acid, drop for 30 min, control the temperature at 30°C, continue to stir for 1.5 h, then add 5 parts of zinc nitrate, and stir for 15 min to prepare the B component;

[0053] S4, the B component is added to the A component at a rate of 1 mL / s, stirred at 700 r / min for 35 min to ensure uniform mixing; then transferred into a sand mill, 1 mm diameter zirconium beads are added, the mass ratio of the system is 3:1, and grinding is carried out at 1800 r / min for 2.5 h, the temperature is controlled at 30°C in the initial 1 h, and the temperature is controlled at 35°C in the subsequent 1-2.5 h, the particle size is controlled at 7-9 μm, and a filter bag with a pore size of 150 μm is used for filtration, after filtration, the viscosity is detected at 25°C with a ZO-4 cup, isopropanol is used to adjust to 70 s, and phosphoric acid is used to adjust the pH to 5, to obtain the anti-skid inorganic zinc coating.

[0054] Example 3, preparation of anti-skid inorganic zinc coating, the specific preparation steps are as follows:

[0055] S1, dry the zinc powder, titanium dioxide, and mica powder at 105°C for 2.5h; activate the fumed silica at 125°C for 1.5h;

[0056] S2, 20 parts of deionized water, 14 parts of isopropyl alcohol, 4 parts of ethylene glycol were added into a dispersion kettle, stirred at 550 r / min for 8 min, then 70 parts of zinc powder, 8 parts of titanium dioxide, 7 parts of mica powder, 5 parts of fumed silica, 3 parts of silica-coated aluminum powder were added in turn, stirred for 18 min after adding each raw material, finally 20 parts of zinc phosphate and 15 parts of wollastonite were added, stirred for 35 min, to prepare A component;

[0057] S3, 30 parts of tetraethyl orthosilicate were added into another reaction kettle, stirred at 350 r / min, 6 parts of phosphoric acid were slowly added dropwise, and the dropping was completed in 25 min, the temperature was controlled at 27℃, and the stirring was continued for 1.2 h, then 4 parts of zinc nitrate were added, stirred for 12 min, to prepare B component;

[0058] S4, B component was added to A component at a rate of 1 mL / s, stirred at 650 r / min for 32 min to ensure uniform mixing; then transferred into a sand mill, added zirconium beads with a diameter of 1 mm, and the mass ratio of the system was 3:1, and ground at 1650 r / min for 2.2 h, the temperature was controlled at 27℃ in the initial 1 h, and the temperature was controlled at 32℃ in the subsequent 1-2.2 h, the particle size was controlled at 7-9 μm, and the filter bag with a pore size of 150 μm was used for filtration, after filtration, the viscosity was detected at 25℃ with a Zeeol-4 cup, adjusted to 65 s with isopropyl alcohol, and the pH was adjusted to 4.5 with phosphoric acid, to obtain the anti-skid inorganic zinc coating.

[0059] Example 4, preparation of modified zinc phosphate, the specific preparation steps are as follows:

[0060] A1, 20g of zinc phosphate was weighed into a beaker, 35mL of deionized water was added, and stirred with a magnetic stirrer at 300r / min for 20min to form a uniform suspension; 7mL of silane coupling agent KH-560 and 2.5g of lignin were measured, 4mL of ethanol was added, and ultrasonic dispersion was carried out at 250W for 10min to prepare a modifier solution, the modifier solution was poured into the suspension, and stirred at 350r / min in a constant temperature water bath at 60℃ for 2.5h, then filtered with a Buchner funnel, the filter cake was washed with a mixture of ethanol-water with a volume ratio of 1:1 for 3 times, and finally dried at 75℃ under vacuum for 4h to obtain the first modified zinc phosphate;

[0061] A2, 20g of the first modified zinc phosphate was taken, 50mL of anhydrous ethanol was added, and a stable dispersion was formed by ultrasonic dispersion at 300W power for 20min in a three-necked flask, 11mL of tetraethyl orthosilicate was added dropwise at a rate of 1 drop per second, and 1mol / L hydrochloric acid was added dropwise synchronously to adjust the pH to 3, and the stirring was maintained at 300r / min, the reaction was carried out at 68℃ under reflux for 3h, after cooling, centrifugation was carried out for 15min, the precipitate was washed with anhydrous ethanol for 3 times, and then dried at 105℃ with air blowing for 3.5h, and then sieved through a 200 mesh sieve to obtain the second modified zinc phosphate;

[0062] A3, 20 g of the second modified zinc phosphate was weighed, 25 mL of deionized water was added to form a suspension, 3.5 g of lanthanum nitrate was added and stirred until completely dissolved, 10% ammonia water was added dropwise to adjust the pH to 8.5, and the temperature was raised to 80°C for 2 h. After filtration, the filter cake was washed with deionized water until neutral, and then placed in a muffle furnace at a rate of 4°C / min to 380°C for calcination for 1.2 h. After natural cooling, the modified zinc phosphate was obtained.

[0063] Example 5, preparation of modified zinc phosphate, the specific preparation steps are as follows:

[0064] A1, 20 g of zinc phosphate was weighed into a beaker, 45 mL of deionized water was added, and stirred with a magnetic stirrer at 350 r / min for 30 min to form a uniform suspension; 9 mL of silane coupling agent KH-560 and 3.5 g of lignin were weighed, 6 mL of ethanol was added, and ultrasonic dispersion was carried out at 250 W for 20 min to prepare a modifier solution. The modifier solution was poured into the suspension, and stirred at 400 r / min in a constant temperature water bath at 70°C for 3.5 h. Then, the mixture was filtered with a Buchner funnel, the filter cake was washed with a mixture of ethanol and water (1:1 by volume) for 4 times, and finally dried at 85°C under vacuum for 5 h to obtain the first modified zinc phosphate.

[0065] A2, 20 g of the first modified zinc phosphate was taken, 60 mL of anhydrous ethanol was added, and a stable dispersion was formed by ultrasonic dispersion at 300 W for 25 min in a three-necked flask. 13 mL of tetraethyl orthosilicate was added at a rate of 1 drop per second, and 1 mol / L hydrochloric acid was added synchronously to adjust the pH to 4. The stirring speed was maintained at 300 r / min, and the reaction was carried out at 72°C under reflux for 4 h. After cooling, centrifugation was carried out for 15 min, the precipitate was washed with anhydrous ethanol for 4 times, and then dried at 115°C for 4.5 h. Finally, the second modified zinc phosphate was obtained by passing through a 200 mesh sieve.

[0066] A3, 20 g of the second modified zinc phosphate was weighed, 35 mL of deionized water was added to form a suspension, 4.5 g of lanthanum nitrate was added and stirred until completely dissolved, 10% ammonia water was added dropwise to adjust the pH to 9.5, and the temperature was raised to 90°C for 3 h. After filtration, the filter cake was washed with deionized water until neutral, and then placed in a muffle furnace at a rate of 6°C / min to 420°C for calcination for 1.8 h. After natural cooling, the modified zinc phosphate was obtained.

[0067] Example 6, preparation of modified wollastonite, the specific preparation steps are as follows:

[0068] B1, 15 g of wollastonite was weighed into a beaker, 135 mL of a mixed acid prepared by mixing 10% hydrochloric acid and 5% citric acid was added, and the mixture was stirred at 300 r / min in a constant temperature water bath at 78°C for 4.5 h. After filtration, the filter cake was washed with deionized water until the pH was 7, and then dried at 70°C under vacuum for 4.5 h to obtain the first modified wollastonite.

[0069] B2, take 15g of the first modified wollastonite, add 110mL of deionized water and ultrasonic dispersion for 20min with 300W power, transfer into a four-necked flask, add 3mL of styrene, 2mL of butyl acrylate, 0.7g of ammonium persulfate, stir at 300r / min under nitrogen protection at 73℃ for 3.5h, centrifuge for 15min after cooling, wash the precipitate with deionized water for 2 times, dry at 95℃ for 4h, and then sieve 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 to form a suspension, drop 18mL of barium chloride solution with a concentration of 0.8mol / L and stir for 8min, drop 17mL of sodium sulfate solution with a concentration of 0.8mol / L in 14min, stir at 250r / min at 28℃ for 1.8h, after reaction, filter, wash the filter cake with deionized water until no chloride ions are detected in the filtrate, and finally dry at 85℃ with air blowing for 3.5h to obtain the modified wollastonite.

[0071] Example 7, preparation of modified wollastonite, the specific preparation steps are as follows:

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

[0073] B2, take 15g of the first modified wollastonite, add 130mL of deionized water and ultrasonic dispersion for 30min with 300W power, transfer into a four-necked flask, add 4mL of styrene, 3mL of butyl acrylate, 0.9g of ammonium persulfate, stir at 350r / min under nitrogen protection at 77℃ for 4.5h, centrifuge for 15min after cooling, wash the precipitate with deionized water for 3 times, dry at 105℃ for 5h, and then sieve 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 to form a suspension, drop 22mL of barium chloride solution with a concentration of 0.8mol / L and stir for 12min, drop 19mL of sodium sulfate solution with a concentration of 0.8mol / L in 16min, stir at 300r / min at 32℃ for 2.2h, after reaction, filter, wash the filter cake with deionized water until no chloride ions are detected in the filtrate, and finally dry at 95℃ with air blowing for 4.5h to obtain the modified wollastonite.

[0075] Comparative Example 1, preparation of anti-skid inorganic zinc coating, the specific preparation steps are as follows:

[0076] The remaining steps are unchanged, only the zinc phosphate of Example 3 is replaced with the modified zinc phosphate prepared in Example 4, to prepare the anti-skid inorganic zinc coating.

[0077] The anti-skid inorganic zinc coating is prepared, and the specific preparation steps are as follows:

[0078] The remaining steps are unchanged, only the wollastonite of Example 3 is replaced with the modified wollastonite prepared in Example 7, to prepare the anti-skid inorganic zinc coating.

[0079] The anti-skid inorganic zinc coating is prepared, and the specific preparation steps are as follows:

[0080] The remaining steps are unchanged, only the zinc phosphate of 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 the anti-skid inorganic zinc coating.

[0081] Performance test

[0082] Test item Test standard Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Anti-skid performance (friction coefficient) GB / T9263-2020 Dry: 0.58 Wet: 0.42 Oil: 0.35 Dry: 0.61 Wet: 0.45 Oil: 0.38 Dry: 0.65 Wet: 0.48 Oil: 0.41 Dry: 0.72 Wet: 0.55 Oil: 0.48 Dry: 0.78 Wet: 0.62 Oil: 0.55 Dry: 0.85 Wet: 0.70 Oil: 0.63 Anti-corrosion performance (1000h neutral salt spray test) GB / T1771-2007 Local point rust, rust area 8.5%; adhesion 4 levels A small amount of point rust, rust area 6.2%; adhesion 3 levels Edge trace rust, rust area 3.8%; adhesion 2 levels No obvious rust, local slight loss of luster; adhesion 1 level No rust, local slight loss of luster; adhesion 1 level No rust, good gloss retention; adhesion 1 level Hardness GB / T6739-2022 HB level H level 2H level 3H level 4H level 5H level Impact strength GB / T1732-2020 20kg·cm 25kg·cm 30kg·cm 38kg·cm 45kg·cm 55kg·cm Room temperature sedimentation rate HG / T4759-2014 Room temperature standing for 30d: 12.5% Room temperature standing for 30d: 9.8% Room temperature standing for 30d: 6.3% Room temperature standing for 30d: 3.1% Room temperature standing for 30d: 2.5% Room temperature standing for 60d: 0.8% Low temperature stability HG / T4759-2014 -5℃ standing for 7d: a small amount of stratification -5℃ standing for 7d: no obvious stratification -5℃ standing for 7d: no stratification -5℃ standing for 15d: no stratification -5℃ standing for 15d: no stratification -5℃ standing for 30d: no stratification

[0083] According to the performance test data, the performance of the anti-skid inorganic zinc coating shows a significant improvement trend with the modification of raw materials and the optimization of the formula: in terms of anti-skid performance, the friction coefficients of Examples 1-3 are lower, while the friction coefficients of Comparative Examples 1-3 using modified zinc phosphate, modified wollastonite, and both are significantly higher, reaching 0.85, 0.70, and 0.63 respectively in dry, humid, and oily environments; in terms of corrosion resistance, Examples 1-3 have different degrees of rust after 1000h of neutral salt spray testing (rust area 3.8%-8.5%, adhesion 2-4 levels), while Comparative Examples 1-3 have no rust or only slight loss of gloss, and the adhesion reaches level 1; in terms of hardness and impact strength, Examples 1-3 are HB-2H, 20-30kg・cm respectively, and Comparative Examples 1-3 are improved to 3H-5H, 38-55kg・cm; in terms of stability, Examples 1-3 have a sedimentation rate of 6.3%-12.5% at room temperature for 30d, and some layering at -5℃ for 7d, while Comparative Example 3 has a sedimentation rate of only 0.8% at room temperature for 60d, and no layering at -5℃ for 30d, overall showing that the modification of raw materials can greatly improve the anti-skid, corrosion resistance, mechanical properties, and stability of the coating.

[0084] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements or use similar methods to replace the described specific embodiments, as long as they do not deviate from the scope of the invention or exceed the scope defined by the present claims.

Claims

1. An anti-slip inorganic zinc coating, characterized in that: The raw materials include 65-75 parts of zinc powder, 6-10 parts of titanium white powder, 6-8 parts of mica powder, 18-22 parts of deionized water, 15-20 parts of isopropyl alcohol, 3-5 parts of ethylene glycol, 12-18 parts of modified wollastonite, 4-6 parts of fumed silica, 2-4 parts of silicon dioxide coated aluminum powder, 18-22 parts of modified zinc phosphate, 28-32 parts of tetraethyl orthosilicate, 5-7 parts of phosphoric acid, and 4-6 parts of zinc nitrate.

2. The anti-skid inorganic zinc coating according to claim 1, characterized in that: The particle size of the zinc powder is 10-20 μm, and the zinc powder is subjected to surface degreasing treatment. The specific steps of the degreasing treatment are as follows: the zinc powder is added into a sodium hydroxide solution with a mass fraction of 8%, stirred at 250 r / min for 20 min at 45°C, then washed with deionized water until neutral, and dried at 95°C with air blowing for 3 h.

3. The anti-skid inorganic zinc coating according to claim 1, characterized in that: The silicon dioxide coated aluminum powder is flaky aluminum powder with a diameter-thickness ratio of 50-80:1, and the surface is coated with a silicon dioxide protective film with a mass fraction of 2%. The protective film is prepared as follows: 100 g of aluminum powder is dispersed in 500 mL of an ethanol-water mixed solution with a volume ratio of 3:1, 0.5 g of silane coupling agent KH-550 is added, stirred at 30°C for 30 min, then 6 g of tetraethyl orthosilicate and 1.2 mL of hydrochloric acid are added to form a mixture with a pH of 4.5, the temperature is controlled at 50°C, and the reaction is carried out at 300 r / min for 2 h, then the temperature is increased to 80°C and the reaction is carried out for 1 h, after centrifugal washing, vacuum drying is carried out at 60°C for 2 h.

4. The anti-skid inorganic zinc coating according to claim 1, characterized in that: The modified zinc phosphate is prepared according to the following specific steps: A1, the zinc phosphate is weighed and put into a beaker, deionized water is added, and a magnetic stirrer with a speed of 300-350 r / min is used for stirring for 20-30 min to form a uniform suspension; the silane coupling agent KH-560 and lignin are measured, ethanol is added, and ultrasonic dispersion is carried out at 250 W for 10-20 min to prepare a modifier solution; the modifier solution is poured into the suspension, and stirring is carried out at 350-400 r / min in a constant temperature water bath at 60-70°C for 2.5-3.5 h; then, the mixture is filtered through a Buchner funnel, the filter cake is washed with an ethanol-water mixture with a volume ratio of 1:1 for 3-4 times, and finally vacuum drying is carried out at 75-85°C for 4-5 h to obtain the first modified zinc phosphate; A2, the first modified zinc phosphate is taken, anhydrous ethanol is added, and ultrasonic dispersion is carried out at 300 W in a three-necked flask for 20-25 min to form a stable dispersion liquid; tetraethyl orthosilicate is added at a rate of 1 drop per second, and 1 mol / L hydrochloric acid is added synchronously to adjust the pH to 3-4; stirring is carried out at 300 r / min, and the reaction is carried out at 68-72°C under reflux for 3-4 h; after cooling, centrifugal washing is carried out for 15 min, the precipitate is washed with anhydrous ethanol for 3-4 times, air drying is carried out at 105-115°C for 3.5-4.5 h, and then the mixture is sieved through a 200 mesh sieve to obtain the second modified zinc phosphate. A3, the second modified zinc phosphate is weighed, added into deionized water to form a suspension, added into lanthanum nitrate to stir until completely dissolved, added into 10% ammonia water to adjust pH to 8.5-9.5, heated to 80-90℃ to react for 2-3h, after filtration, the filter cake is washed with deionized water until neutral, put into a muffle furnace to heat to 380-420℃ at a rate of 4-6℃ / min to calcine for 1.2-1.8h, naturally cooled to obtain modified zinc phosphate.

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

6. The anti-skid inorganic zinc coating according to claim 1, characterized in that: The modified wollastonite is prepared according to the following steps: B1, the wollastonite is weighed and put into a beaker, added into a mixed acid composed of hydrochloric acid and citric acid, stirred at 300-350r / min under a constant temperature water bath of 78-82℃ for 4.5-5.5h, after filtration, the filter cake is washed with deionized water until pH=7, vacuum dried at 70-80℃ for 4.5-5.5h to obtain the first modified wollastonite; B2, the first modified wollastonite is taken, added into deionized water to ultrasonically disperse for 20-30min at a power of 300W, transferred into a four-necked flask, added into styrene, butyl acrylate and ammonium persulfate, stirred at 300-350r / min under nitrogen protection at 73-77℃ for 3.5-4.5h, after cooling, centrifuged for 15min, the precipitate is washed with deionized water for 2-3 times, dried at 95-105℃ for 4-5h and then sieved through a 300 mesh sieve to obtain the second modified wollastonite; B3, the second modified wollastonite is taken, added into deionized water to form a suspension, added into a barium chloride solution with a concentration of 0.8mol / L to stir for 8-12min, added into a sodium sulfate solution with a concentration of 0.8mol / L dropwise, stirred at 250-300r / min at 28-32℃ for 1.8-2.2h, after reaction, filtered, the filter cake is washed with deionized water until no chloride ion is detected in the filtrate, finally dried at 85-95℃ for 3.5-4.5h to obtain the modified wollastonite.

7. The anti-skid inorganic zinc coating according to claim 6, characterized in that: The amount ratio of the wollastonite and the mixed acid in B1 is 15g:170-190mL; wherein the mixed acid is prepared from 135-145mL of 10% hydrochloric acid and 35-45mL of 5% citric acid; The amount 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 amount ratio of the second modified wollastonite in B3, deionized water, barium chloride solution, sodium sulfate solution is 15g:75-85mL:18-22mL:17-19mL.

8. A process for the preparation of a non-slip inorganic zinc coating, characterized in that: Specifically comprising the following steps: S1, dry the zinc powder, titanium dioxide powder and mica powder at 100-110°C for 2-3h; activate the fumed silica at 120-130°C for 1-2h; S2, add 18-22 parts of deionized water, 12-16 parts of isopropanol and 3-5 parts of ethylene glycol into a dispersion kettle, stir at 500-600r / min for 5-10min, then add 65-75 parts of zinc powder, 6-10 parts of titanium dioxide powder, 6-8 parts of mica powder, 4-6 parts of fumed silica, 2-4 parts of silica-coated aluminum powder, stir for 15-20min after adding each raw material, finally add 18-22 parts of modified zinc phosphate and 12-18 parts of modified wollastonite, stir for 30-40min, to prepare the A component; S3, add 28-32 parts of tetraethyl orthosilicate into another reaction kettle, stir at 300-400r / min, slowly drop 5-7 parts of phosphoric acid, drop for 20-30min, control the temperature at 25-30°C, continue to stir for 1-1.5h, then add 4-5 parts of zinc nitrate, stir for 10-15min, to prepare the B component; S4, add the B component into the A component at a speed of 1mL / s, stir at 600-700r / min for 30-35min to ensure uniform mixing; Then transfer into a sand mill, add zirconium beads with a diameter of 1mm, with a mass ratio of 3:1, grind at 1500-1800r / min for 2-2.5h, control the particle size at 7-9μm, filter with a filter bag with a pore size of 150μm, after filtration, detect the viscosity at 25°C with a co-4 cup, adjust to 60-70s with isopropanol, adjust the pH to 4-5 with phosphoric acid, to obtain the anti-slip inorganic zinc coating.

9. The method for preparing an anti-slip inorganic zinc coating according to claim 1, characterized in that: During the sand mill grinding process, a segmented temperature control method is adopted, the temperature is controlled at 25-30°C within the first 1h, and the temperature is controlled at 30-35°C in the subsequent period, which can not only protect the initial performance of the material, but also improve the grinding efficiency and particle size uniformity in the later period, finally ensure the stability and anti-slip, corrosion resistance and other core properties of the coating system.