Self-repairing inorganic resin anticorrosive coating and preparation method thereof

Abstract

The application discloses a kind of self-repairing inorganic resin anticorrosive paint and preparation method, belong to anticorrosive paint technical field.The paint includes inorganic resin 30-50%, nano-grade silicon dioxide 5-10%, zinc phosphomolybdate 10-20%, functional filler 20-30% by mass percentage, and the balance is deionized water.Preparation method includes high-speed dispersion, step-by-step stirring, temperature control and other steps, without adding zinc powder, solve the environmental protection and cost problem caused by zinc powder;Through multi-step preparation process optimization, realize the uniform dispersion of each component, improve the film compactness of coating, can quickly form self-repairing protective film when corroded, cost-effective, strong practicality.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion coating technology, specifically to a self-healing inorganic resin anti-corrosion coating and its preparation method. Background Technology

[0002] Anti-corrosion coatings are widely used for surface protection of metal components and equipment, effectively delaying metal corrosion and extending service life. Currently, traditional inorganic anti-corrosion coatings mostly use zinc powder as the core anti-corrosion component. Zinc powder has become a commonly used anti-corrosion material in the industry due to its cathodic protection and self-healing functions. However, zinc powder is harmful to the human body and easily causes environmental pollution. Moreover, the limited availability of zinc resources leads to large price fluctuations. Therefore, the industry urgently needs an environmentally friendly anti-corrosion coating that can replace zinc powder and has anti-corrosion and self-healing functions.

[0003] In existing inorganic anti-corrosion coatings, some products attempt to improve anti-corrosion performance by adding various additives. However, these often suffer from problems such as uneven component dispersion, poor film density, and slow self-healing response. Furthermore, some preparation processes are complex and costly, making it difficult to meet the needs of large-scale industrial applications. Simultaneously, in existing preparation processes, the mixing of components is prone to agglomeration and insufficient fusion, leading to unstable coating performance and failing to achieve ideal anti-corrosion and self-healing effects. Summary of the Invention

[0004] The purpose of this invention is to provide a self-healing inorganic resin anti-corrosion coating and its preparation method, which eliminates the need for zinc powder, thus solving the environmental, health, and cost problems associated with zinc powder. At the same time, by optimizing the preparation process, the components are uniformly dispersed, improving the film density and self-healing performance of the coating.

[0005] The above-mentioned technical objective of the present invention is achieved through the following technical solution: A self-healing inorganic resin anti-corrosion coating, comprising, by mass percentage: 30-50% inorganic resin, 5-10% nano-sized silica, 10-20% zinc phosphomolybdate, 20-30% functional filler, with the balance being deionized water, and the sum of the mass percentages of each component being 100%.

[0006] In a preferred embodiment, the inorganic resin is a silane-modified inorganic resin with a molecular weight of 500-2000 Daltons, and the nano-sized silica has a particle size of 50-200 nm.

[0007] A method for preparing a self-healing inorganic resin anti-corrosion coating, the method comprising the following steps: (1) Weigh 30-50% inorganic resin and 5-10% nano-sized silica by mass percentage, and disperse them at high speed for ≥30 min until the mixture is a uniform paste. (2) Add 10-20% zinc phosphomolybdate and 20-30% functional filler to the uniform paste system obtained in step (1) by mass percentage, then add deionized water to adjust the viscosity of the system, and mix evenly to obtain the self-healing inorganic resin anti-corrosion coating.

[0008] In a preferred embodiment, before high-speed dispersion in step (1), nano-sized silica is pretreated at 80-100°C for 15-20 minutes, and immediately after pretreatment, it is mixed with inorganic resin for high-speed dispersion.

[0009] In a preferred embodiment, the high-speed dispersion rotation speed in step (1) is 800-1200 r / min.

[0010] In a preferred embodiment, the amount of deionized water added in step (2) is based on adjusting the viscosity of the coating system to 2000-5000 mPa·s, and after addition, it is stirred evenly so that the components are dispersed uniformly.

[0011] In a preferred embodiment, after adding zinc phosphomolybdate and functional filler in step (2), the mixture is first stirred at low speed for 5-8 minutes, then deionized water is added to adjust the viscosity and stirred at high speed for 10-15 minutes. The low-speed stirring speed is 200-300 r / min, and the high-speed stirring speed is 800-1200 r / min. In a preferred embodiment, during the low-speed stirring stage, the temperature of the stirring system is controlled to be maintained at 30-35°C, and during the high-speed stirring stage, the temperature of the stirring system is controlled to be maintained at 45-50°C. Furthermore, a settling transition time of 1-2 minutes is provided after the low-speed stirring ends and before the high-speed stirring begins.

[0012] In a preferred embodiment, the uniform paste system obtained in step (1) is kept at 40-50°C for 20-30 minutes, and a low-speed stirring of 50-80 r / min is used during the heat preservation process. After the heat preservation is completed, step (2) is then performed.

[0013] In a preferred embodiment, during the heat preservation process, the paste system is subjected to a vacuum pumping-vacuum breaking operation every 5-7 minutes. The vacuum pumping pressure is controlled at -0.05 to -0.06 MPa, the pumping time is 10-15 seconds, and the pressure is restored to normal after the vacuum is broken.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. The coating of this invention does not require the addition of zinc powder, which completely solves the problems of zinc powder being harmful to the human body, polluting the environment, and having large price fluctuations. It uses inorganic resin and nano-grade silica as the skeleton and zinc phosphomolybdate as the self-healing functional component. It is environmentally friendly, cost-effective, and meets the needs of industry development. 2. Zinc phosphomolybdate in the coating can release molybdate ions when corrosive media penetrate into the metal substrate and trigger local electrochemical reactions that cause pH changes. These ions react with Fe²⁺ and Fe³⁺ generated on the substrate surface to form an insoluble iron molybdate protective film, effectively covering the anodic area, achieving self-repair, and providing excellent corrosion protection. 3. The preparation process is simple, requiring no complex equipment, and can be industrialized on a large scale. The coating film has good density and uniform performance, fast self-healing response, and strong practicality. It can be widely used for corrosion protection of various metal components. Detailed Implementation

[0015] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they are within the scope of the claims of the present invention. Example

[0016] A self-healing inorganic resin anti-corrosion coating comprises, by mass percentage: 30-50% inorganic resin, 5-10% nano-sized silica, 10-20% zinc phosphomolybdate, 20-30% functional filler, and the balance being deionized water, with the sum of the mass percentages of each component being 100%.

[0017] Weigh each component according to the above-mentioned mass percentages. Inorganic resin serves as the matrix skeleton of the coating, nano-sized silica is dispersed in the inorganic resin as a reinforcing component, zinc phosphomolybdate serves as a self-healing functional component, functional fillers are used to assist in improving the film-forming performance of the coating, and deionized water is used to adjust the overall viscosity of the coating to suit the construction requirements. After the components are mixed in the specified proportions, a stable coating system can be formed. The skeleton structure constructed by inorganic resin and nano-sized silica can improve the density of the coating film. Zinc phosphomolybdate can play a self-healing role when the coating is applied to the surface of a metal substrate and is penetrated by corrosive media. Functional fillers further optimize the mechanical properties and construction performance of the coating. The components work synergistically to achieve excellent anti-corrosion and self-healing effects without the addition of zinc powder, while avoiding the environmental and cost problems caused by zinc powder. Moreover, the proportions of each component are clearly defined, and each component can be accurately weighed according to the actual construction requirements to prepare an anti-corrosion coating that meets the requirements.

[0018] In the above-mentioned self-healing inorganic resin anti-corrosion coating, the inorganic resin is a silane-modified inorganic resin with a molecular weight of 500-2000 Daltons and a particle size of 50-200 nm for nano-sized silica.

[0019] Silane-modified inorganic resins with a molecular weight range of 500-2000 Daltons are selected. Silane-modified inorganic resins in this molecular weight range possess both good flowability and film-forming properties. The introduction of silane groups can enhance the compatibility between the inorganic resin and nano-sized silica, avoiding stratification and agglomeration when the two are mixed. Nano-sized silica with a particle size of 50-200 nm is selected. Nano-sized silica in this particle size range can fully utilize the reinforcing effect of nanoparticles, improving the density and wear resistance of the coating film, while avoiding agglomeration problems caused by excessively small particle size, and also avoiding the impact of excessively large particle size on the smoothness of the coating film. Selecting suitable silane-modified inorganic resins and nano-sized silica, and combining them with other components to prepare coatings, can effectively improve the system stability and overall performance of the coating. Example

[0020] A method for preparing a self-healing inorganic resin anti-corrosion coating, comprising the following steps: (1) Weigh 30-50% inorganic resin and 5-10% nano-sized silica by mass percentage, and disperse them at high speed for ≥30 min until the mixture is a uniform paste. (2) Add 10-20% zinc phosphomolybdate and 20-30% functional filler to the uniform paste system obtained in step (1) by mass percentage, then add deionized water to adjust the viscosity of the system, and mix evenly to obtain the self-healing inorganic resin anti-corrosion coating.

[0021] In the preparation process, inorganic resin and nano-sized silica are accurately weighed according to the specified mass percentages. The two components are then placed in a dispersion device for high-speed dispersion for at least 30 minutes. The shear force generated by the high-speed dispersion breaks down the agglomerates of nano-sized silica, allowing it to be uniformly dispersed in the inorganic resin until a paste-like system with no obvious particles and a uniform texture is formed. This process ensures that the inorganic resin and nano-sized silica are fully combined, laying the foundation for the subsequent coating performance. Subsequently, zinc phosphomolybdate and functional fillers are added to the paste-like system according to the corresponding mass percentages, ensuring that the two fillers are evenly spread on the surface of the system. Then, deionized water is gradually added while stirring. The amount of deionized water added is adjusted according to the viscosity of the system until the viscosity reaches the standard for application. After uniform mixing, the target anti-corrosion coating is obtained. The entire preparation process is logically clear and the operation is well-defined. The parameters and operation methods of each step are clearly defined. By following these steps, a self-healing inorganic resin anti-corrosion coating that meets the requirements can be successfully prepared. Moreover, this preparation process does not require complex equipment and can achieve large-scale production.

[0022] In the above preparation method, before high-speed dispersion in step (1), nano-sized silica is pretreated at 80-100℃ for 15-20 min, and immediately mixed with inorganic resin for high-speed dispersion after pretreatment.

[0023] Before the high-speed dispersion operation in step (1), nano-sized silica is placed in a heating device and the temperature is controlled between 80-100℃ for 15-20 minutes for pretreatment. This temperature and time pretreatment can quickly remove the moisture adsorbed on the surface of nano-sized silica, preventing the hydroxyl groups on the surface of nano-sized silica from agglomerating due to moisture, thus preventing the problem of agglomerates that are difficult to break during high-speed dispersion. After the pretreatment, the nano-sized silica is immediately mixed with inorganic resin. At this time, the surface of nano-sized silica is in a dry state, which can better contact and fuse with inorganic resin, reducing the interfacial tension between the two. During subsequent high-speed dispersion, the uniform dispersion of nano-sized silica in inorganic resin can be achieved more efficiently, avoiding secondary agglomeration. By controlling the pretreatment temperature and time with conventional heating equipment, this method can effectively improve the mixing uniformity of inorganic resin and nano-sized silica, providing a guarantee for the subsequent performance improvement of the coating.

[0024] In the above preparation method, the high-speed dispersion rotation speed in step (1) is 800-1200 r / min.

[0025] In the high-speed dispersion process of step (1), the speed of the dispersion equipment is adjusted to 800-1200 r / min. This speed range can generate sufficient shear force to effectively break the agglomerates of nano-sized silica, so that the nano-sized silica is uniformly dispersed in the inorganic resin. It can also avoid the destruction of the molecular structure of the inorganic resin due to excessive speed, and prevent the resin from undergoing local cross-linking, which would affect the film-forming performance of the coating. At the same time, it can also avoid the problem of insufficient dispersion and particle agglomeration due to excessively low speed. By adjusting the speed knob of the dispersion equipment, the speed is controlled within this limited range. With a dispersion time of not less than 30 minutes, a uniform paste system can be obtained. The operation is simple and controllable.

[0026] In the above preparation method, the amount of deionized water added in step (2) is based on adjusting the viscosity of the coating system to 2000-5000 mPa·s, and after addition, it is stirred evenly so that the components are dispersed uniformly.

[0027] In step (2), after adding zinc phosphomolybdate and functional fillers, deionized water is gradually added while continuously stirring. During the process, the viscosity of the system is monitored in real time using a viscometer until the viscosity of the system is adjusted to 2000-5000 mPa·s. This viscosity range ensures that the coating has good workability, which is convenient for brushing, spraying and other construction operations. At the same time, it can avoid the problems of sagging and uneven thickness after the coating film is formed due to excessively low viscosity, and it can also avoid the problems of construction difficulties and uneven film formation due to excessively high viscosity. After adding deionized water, continuous stirring can ensure that the deionized water penetrates evenly into the interior of the system, avoid the agglomeration of zinc phosphomolybdate and functional fillers due to local viscosity differences, and make the components dispersed evenly in the system, ensuring uniform performance of the coating in all areas. By measuring the viscosity with a conventional viscometer and adjusting the amount of deionized water added in this way and stirring, the viscosity of the system can be accurately controlled and the components can be evenly dispersed.

[0028] In the above preparation method, after adding zinc phosphomolybdate and functional filler in step (2), the mixture is first stirred at low speed for 5-8 minutes, then deionized water is added to adjust the viscosity and stirred at high speed for 10-15 minutes. The low-speed stirring speed is 200-300 r / min and the high-speed stirring speed is 800-1200 r / min.

[0029] In step (2), after adding zinc phosphomolybdate and functional filler, first adjust the speed of the stirring equipment to 200-300 r / min and perform low-speed stirring for 5-8 minutes. This low-speed stirring at this speed and time allows zinc phosphomolybdate and functional filler to slowly and evenly spread on the surface of the paste system obtained in step (1), avoiding the two fillers from agglomerating due to rapid stirring. At the same time, it can reduce the impact force between the filler and the paste system, preventing damage to the stable structure formed by inorganic resin and nano-sized silica. After the low-speed stirring is completed, add deionized water to adjust the viscosity, and then increase the speed to 800-1200 r / min and perform high-speed stirring for 10-15 minutes. Through high-speed shear force, zinc phosphomolybdate and functional filler can fully penetrate into the paste system, achieving deep fusion of each component and avoiding excessively high local concentrations or agglomeration. By adjusting the speed and time of the stirring equipment and following this step, the mixing uniformity of each component can be effectively improved, ensuring the stability of the coating performance.

[0030] In the above preparation method, during the low-speed stirring stage, the temperature of the stirring system is controlled to be maintained at 30-35℃, and during the high-speed stirring stage, the temperature of the stirring system is controlled to be maintained at 45-50℃. In addition, a standing transition time of 1-2 minutes is set after the low-speed stirring ends and before the high-speed stirring begins.

[0031] In the low-speed stirring stage of step (2), the temperature of the stirring system is controlled at 30-35℃ using conventional temperature control equipment. This temperature range can prevent zinc phosphomolybdate and functional fillers from agglomerating prematurely due to excessive temperature, while maintaining the stable viscosity of the inorganic resin, ensuring that the two fillers are evenly spread on the surface of the paste system, and improving the initial mixing effect. After the low-speed stirring is completed, stirring is stopped and the system is left to stand for 1-2 minutes to allow the spread fillers to adhere stably to the surface of the system, preventing the fillers from being dispersed by shear force during subsequent high-speed stirring, thus laying the foundation for deep fusion. After standing, the high-speed stirring stage is entered, and the system temperature is adjusted to 45-50℃. This temperature can moderately reduce the viscosity of the inorganic resin, enhance its encapsulation of the fillers, and promote the interfacial bonding between the inorganic resin and the fillers, thereby improving the fusion effect. Moreover, this temperature will not cause cross-linking of the inorganic resin or secondary agglomeration of nano-sized silica. Temperature control is achieved by using conventional temperature control equipment. By operating in this way, the mixing uniformity of each component can be further improved, ensuring the balanced performance of the coating.

[0032] In the above preparation method, the uniform paste system obtained in step (1) is kept at 40-50℃ for 20-30 minutes. During the heat preservation process, a low-speed stirring of 50-80 r / min is used. After the heat preservation is completed, step (2) is then performed.

[0033] After the high-speed dispersion in step (1), the resulting uniform paste system is transferred to the heat preservation equipment. The heat preservation temperature is controlled at 40-50℃ and the heat preservation is maintained for 20-30 minutes. During the heat preservation process, the stirring equipment is adjusted to a low speed of 50-80r / min. This speed can prevent the secondary agglomeration of nano-sized silica when the paste system is left to stand. At the same time, it can promote the interfacial bonding between inorganic resin and nano-sized silica and enhance the compatibility between the two. The heat preservation temperature of 40-50℃ can maintain the stable viscosity of the paste system and prevent the viscosity of inorganic resin from rising due to a sudden drop in system temperature. This can prevent the problem of difficult fusion when zinc phosphomolybdate and functional fillers are added later. After the heat preservation is completed, the paste system is in a stable state. At this time, the filler is added in step (2). This can ensure that the filler penetrates and fuses quickly and uniformly. This operation is achieved by conventional heat preservation and stirring equipment, which effectively improves the fusion effect and performance stability of each component of the coating.

[0034] In the above preparation method, during the heat preservation process, the paste system is subjected to a vacuum pumping and vacuum breaking operation every 5-7 minutes. The vacuum pumping pressure is controlled at -0.05 to -0.06 MPa, the pumping time is 10-15 seconds, and the pressure is restored to normal after the vacuum is broken.

[0035] During the heat preservation and low-speed stirring process, every 5-7 minutes, connect the heat preservation equipment to the vacuum equipment, adjust the vacuum pumping pressure to -0.05--0.06MPa, continue pumping for 10-15 seconds, then release the vacuum to restore the system to normal pressure, and repeat this operation until the heat preservation is completed; this intermittent vacuum pumping-vacuum breaking operation can quickly remove the trace amount of air remaining in the paste system after the high-speed dispersion in step (1), avoid the oxidation reaction between oxygen in the air and the hydroxyl groups on the surface of nano-sized silica, thereby preventing the compatibility between nano-sized silica and inorganic resin from decreasing, and at the same time, it can prevent the formation of micropores by residual air, which would affect the subsequent film density of the coating; the specific vacuum pressure and pumping time can effectively remove air without causing the paste system to separate or splash, and will not damage the dispersion uniformity of each component. By adjusting the pressure and time with conventional vacuum equipment and operating in this way, the stability of the paste system can be further improved, providing a guarantee for the subsequent filler fusion and coating performance improvement.

[0036] In the above preparation method, the viscosity of deionized water is adjusted by adding it in two stages. The amount of deionized water added in the first stage is 60-70% of the total amount added. After adding it, stir for 3-5 minutes. Then add the remaining 30-40% of deionized water. After adding the deionized water for the second time, control the high-speed stirring speed to be reduced to 600-800 r / min and stir for 5-7 minutes.

[0037] When adjusting the system viscosity in step (2), first calculate the total amount of deionized water to be added. Add 60-70% of the total amount of deionized water for the first time, and continue stirring for 3-5 minutes after adding the water to allow the deionized water to initially penetrate into the system. This avoids the local system becoming too thin due to adding water all at once, and thus prevents zinc phosphomolybdate and functional fillers from agglomerating due to excessively high local concentrations. After the first addition of water and stirring, add the remaining 30-40% of deionized water. At the same time, reduce the high-speed stirring speed from 800-1200 r / min to 600-800 r / min and continue stirring for 5-7 minutes. Reducing the speed can reduce the impact of high-speed shear force on the molecular structure of inorganic resin, avoid resin degradation, and allow the deionized water to diffuse more evenly to all areas of the system, ensuring uniform system viscosity and avoiding performance inconsistencies caused by local viscosity differences. Adding deionized water step by step according to this ratio and speed and time requirements and stirring can effectively improve the stability of the system viscosity and the uniformity of component dispersion, and ensure the quality of coating film formation.

[0038] The test indicators of the coatings prepared in the above embodiments are shown in Table 1 below: Table 1

[0039] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or terminal device that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or terminal device. Unless otherwise specified, an element defined by the phrase "comprising..." or "including..." does not exclude the presence of additional elements in the process, method, article, or terminal device that includes said element. Additionally, in this document, "greater than," "less than," "exceeding," etc., are understood to exclude the stated number; "above," "below," "within," etc., are understood to include the stated number.

[0040] The above description of the embodiments is provided to facilitate understanding and use of the present invention by those skilled in the art. It is obvious to those skilled in the art that various modifications can be easily made to the embodiments, and the general principles described herein can be applied to other embodiments without creative effort. Therefore, the present invention is not limited to the above embodiments. Improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the protection scope of the present invention.

Claims

1. A self-healing inorganic resin anti-corrosion coating, characterized in that, The coating comprises, by mass percentage: 30-50% inorganic resin, 5-10% nano-sized silica, 10-20% zinc phosphomolybdate, 20-30% functional filler, and the balance being deionized water, with the sum of the mass percentages of each component being 100%.

2. The self-healing inorganic resin anti-corrosion coating according to claim 1, characterized in that, The inorganic resin is a silane-modified inorganic resin with a molecular weight of 500-2000 Daltons, and the nano-sized silica has a particle size of 50-200 nm.

3. A method for preparing a self-healing inorganic resin anti-corrosion coating, characterized in that, The preparation method includes the following steps: (1) Weigh 30-50% inorganic resin and 5-10% nano-sized silica by mass percentage, and disperse them at high speed for ≥30 min until the mixture is a uniform paste. (2) Add 10-20% zinc phosphomolybdate and 20-30% functional filler to the uniform paste system obtained in step (1) by mass percentage, then add deionized water to adjust the viscosity of the system, and mix evenly to obtain the self-healing inorganic resin anti-corrosion coating.

4. The preparation method of the self-healing inorganic resin anti-corrosion coating according to claim 3, characterized in that, Before high-speed dispersion in step (1), nano-sized silica is pretreated at 80-100℃ for 15-20 minutes. After pretreatment, it is immediately mixed with inorganic resin for high-speed dispersion.

5. The preparation method of the self-healing inorganic resin anti-corrosion coating according to claim 3, characterized in that, In step (1), the high-speed dispersion rotation speed is 800-1200 r / min.

6. The preparation method of the self-healing inorganic resin anti-corrosion coating according to claim 3, characterized in that, In step (2), the amount of deionized water added should be adjusted to adjust the viscosity of the coating system to 2000-5000 mPa·s, and after adding it, it should be stirred evenly so that the components are dispersed uniformly.

7. The preparation method of the self-healing inorganic resin anti-corrosion coating according to claim 3, characterized in that, In step (2), after adding zinc phosphomolybdate and functional filler, stir at low speed for 5-8 minutes, then add deionized water to adjust the viscosity and stir at high speed for 10-15 minutes. The low-speed stirring speed is 200-300 r / min and the high-speed stirring speed is 800-1200 r / min.

8. The preparation method of the self-healing inorganic resin anti-corrosion coating according to claim 7, characterized in that, During the low-speed stirring stage, the temperature of the stirring system is controlled to be maintained at 30-35℃. During the high-speed stirring stage, the temperature of the stirring system is controlled to be maintained at 45-50℃. After the low-speed stirring ends and before the high-speed stirring begins, a set set time of 1-2 minutes is provided for settling.

9. The preparation method of the self-healing inorganic resin anti-corrosion coating according to claim 3, characterized in that, Place the uniform paste system obtained in step (1) at 40-50℃ for 20-30 minutes, and stir at a low speed of 50-80 r / min during the heat preservation process. After the heat preservation is completed, proceed to step (2).

10. The preparation method of the self-healing inorganic resin anti-corrosion coating according to claim 8, characterized in that, During the heat preservation process, the paste system is subjected to a vacuum pumping and vacuum breaking operation every 5-7 minutes. The vacuum pumping pressure is controlled at -0.05 to -0.06 MPa, the pumping time is 10-15 seconds, and the pressure is restored to normal after the vacuum is broken.

Images