An anti-corrosion and highly weather-resistant alloy resin tile and its preparation process

Abstract

The present invention discloses an anti-corrosion and highly weather-resistant alloy resin tile and its preparation process, which includes the following steps: S1, preparing a basic composite material; S2, adding vanadium oxide and zinc oxide composite nanoparticles prepared by the sol-gel method to the basic composite material; S3, introducing a dynamic cross-linked fluorosilane-based polymer and preparing a surface functional material through a dynamic cross-linking technique; S4, forming a multi-layer structure substrate; S5, preparing a multi-layer co-extruded tile; S6, enhancing the interfacial bonding force of the multi-layer co-extruded tile by using an ultrasonic activation bonding technique; S7, depositing a fluorinated graphene nanofilm by using a plasma-enhanced chemical vapor deposition technique; S8, combining an intelligent monitoring module through a conductive polythiophene composite layer embedded in the bottom layer to complete crack detection and real-time perception of the aging state. The present invention realizes the preparation of an anti-corrosion and highly weather-resistant alloy resin tile by using bio-based materials, multi-layer co-extrusion and intelligent monitoring techniques.

Description

Technical Field

[0001] The present invention relates to the technical field of building materials, and particularly to an anti-corrosion and highly weather-resistant alloy resin tile and its preparation process. Background Art

[0002] In recent years, with the rapid development of the modern construction industry, roofing materials, as an important part of the building structure, have increasingly higher requirements for their performance and functions. Traditional resin tiles used in conventional environments, such as polyvinyl chloride (PVC) tiles, polycarbonate (PC) tiles, and acrylonitrile-styrene-acrylate (ASA) tiles, have become the mainstream choices due to their good mechanical properties and cost advantages. However, with the increasing variability of the global climate and the rise of extreme environments, traditional resin tiles have gradually revealed deficiencies in weather resistance, limited anti-corrosion performance, and single functions, and are unable to meet the long-term stability requirements of modern buildings under harsh conditions such as high ultraviolet radiation, high humidity, and high salt spray.

[0003] In terms of weather resistance, traditional resin tiles usually adopt petrochemical-based materials, which are prone to aging under long-term ultraviolet radiation, such as fading, cracking, and degradation of surface properties. Especially in tropical or plateau regions with strong ultraviolet rays, the service life of traditional roofing materials will be significantly shortened, and it is difficult to maintain long-term structural and aesthetic stability. Although some modified materials enhance weather resistance by adding ultraviolet absorbers or antioxidants, their effects are limited. Especially for building roofing materials exposed to sunlight for a long time, such modification schemes are difficult to provide comprehensive and lasting protection.

[0004] In terms of anti-corrosion performance, building roofing materials are long-term exposed to the natural environment and are easily corroded by acid rain, salt spray, and moisture. Traditional resin tiles have weak resistance to these factors. Especially in coastal areas or areas with serious industrial pollution, salt spray and corrosive gases will accelerate the performance degradation of the roofing materials. This problem not only affects the appearance and service life of the building, but may also cause more serious structural safety problems. In the prior art, the anti-corrosion performance of materials is usually improved by coating corrosion-resistant layers or adding fillers, but these measures are mostly passive protection, and it is difficult to achieve essential corrosion resistance improvement on the material itself. At the same time, their processing costs and complexities are also significantly increased.

[0005] In addition, the functions of traditional resin tiles are relatively single, usually only having basic functions such as sunshading and rain protection, and it is difficult to meet the requirements of modern buildings for multi-functional materials. For example, in terms of self-cleaning, the surfaces of traditional roofing materials are easily covered with dust and pollutants, and frequent cleaning and maintenance are required; in terms of intelligent applications, existing resin tiles have not been able to realize real-time perception and monitoring of their own structural states, such as crack propagation and aging states, and cannot provide timely alarms and maintenance suggestions for users, thus increasing the maintenance costs and management complexities of the building.

[0006] With the growing demand for green and environmentally friendly materials in the construction industry, traditional resin tiles have been widely questioned due to their use of petrochemical-based materials. These materials not only cause resource waste and carbon emissions during production, but also bring serious environmental pollution problems due to their non-degradability at the end of their service life. Although the research on bio-based materials has gradually received attention, their application in the field of roofing tiles is still relatively limited. Existing attempts mainly focus on basic material substitution, and have not been able to develop high-performance and multifunctional tiles by combining the advantages of bio-based materials.

[0007] In terms of processing technology, the manufacturing process of traditional resin tiles mainly relies on the extrusion molding technology of a single-layer material. Although it has a certain production efficiency, it has deficiencies in the integration of multi-layer structures and the realization of complex functions. Some multifunctional tiles attempt to achieve specific functions through multiple processing or coating technologies, but the process is complex and costly. At the same time, the interfacial bonding force between layers is weak, and functional failure is likely to occur due to peeling or crack propagation. In addition, the surface treatment of tiles in existing technologies mostly uses spraying or coating methods, and their durability and functional stability are far inferior to modern processes.

[0008] Therefore, how to provide an anti-corrosion and highly weather-resistant alloy resin tile and its preparation process is an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0009] An object of the present invention is to provide an anti-corrosion and highly weather-resistant alloy resin tile and its preparation process. The present invention combines bio-based polymer materials, dynamic cross-linking technology, multi-layer co-extrusion molding process and intelligent monitoring module to develop an anti-corrosion and highly weather-resistant alloy resin tile. Through the composite reinforcement of polyethylene furanoate and modified potassium titanate whiskers, the weather resistance and anti-corrosion performance of the tile are significantly improved; the ultraviolet shielding and photocatalytic functions are realized by using vanadium oxide and zinc oxide nanoparticles; the introduction of a fluorinated graphene coating provides superhydrophobic self-cleaning ability; the intelligent monitoring module realizes crack detection and aging prediction, and has excellent durability, anti-corrosion, intelligence and environmental protection characteristics.

[0010] According to an embodiment of the present invention, a preparation process of an anti-corrosion and highly weather-resistant alloy resin tile includes the following steps:

[0011] S1. Mix polyethylene furanoate with a toughening agent and an ultraviolet absorber, form a matrix material through melt processing, and uniformly add modified potassium titanate whiskers with fluorine-containing groups grafted on the surface into the matrix material by using ultrasonic dispersion technology to prepare a basic composite material;

[0012] S2. Add vanadium oxide and zinc oxide composite nanoparticles prepared by the sol-gel method to the basic composite material, and perform surface modification on the composite nanoparticles to prepare a composite material with ultraviolet shielding and photocatalytic functions;

[0013] S3. Introduce a dynamically crosslinked fluorosilicon-based polymer into the composite material with ultraviolet shielding and photocatalytic functions, and prepare the surface functional material through the dynamic crosslinking technology;

[0014] S4. Separate the surface functional material, the intermediate layer nanofiber-reinforced composite material, and the bottom conductive polythiophene-based composite material into formed parts, and achieve uniform mixing of multiple components and molecular chain orientation through a dynamic rotary twin-screw extruder to form a multi-layer structure substrate;

[0015] S5. Complete the synchronous co-extrusion molding of the surface layer, intermediate layer, and bottom layer through a three-die extrusion technology to prepare a multi-layer co-extruded tile;

[0016] S6. Enhance the interfacial bonding strength of the multi-layer co-extruded tile by using ultrasonic activation bonding technology;

[0017] S7. Deposit a fluorinated graphene nanomembrane on the surface of the multi-layer co-extruded tile by using plasma-enhanced chemical vapor deposition technology to form a superhydrophobic functional layer;

[0018] S8. Conduct a UV photocatalytic function test on the multi-layer co-extruded tile to verify the reactive oxygen generation ability of the surface nanoparticles, and complete crack detection and real-time perception of the aging state by combining an intelligent monitoring module with the conductive polythiophene composite layer embedded in the bottom layer.

[0019] Optionally, the specific steps of S3 include:

[0020] S31. Place the prepared composite material with ultraviolet shielding and photocatalytic functions in a reaction kettle, add 15%-30% of the dynamically crosslinked fluorosilicon-based polymer based on the total mass of the composite material, start the stirring device of the reaction kettle, raise the temperature to 140 °C, control the stirring speed at 200 rpm, and maintain the stirring time for 30 minutes;

[0021] S32. Add an initiator and an inhibitor during the mixing process. The initiator is benzoyl peroxide, and the dosage is 0.2% of the total mass of the composite material; the inhibitor is hydroquinone, and the dosage is 0.1% of the total mass of the composite material. Continuously stir to cause a preliminary crosslinking reaction of the fluorosilicon-based polymer;

[0022] S33. Connect a dynamic stress loading device to the reaction kettle, apply a shear rate and a shear stress , and set the dynamic stress frequency at 15 Hz, and continuously act for 2 hours to promote the formation of a crosslinked network of the fluorosilicon-based polymer;

[0023] S34. Real-time detect the dynamic mechanical properties of the composite material during the dynamic crosslinking process, monitor the storage modulus and the loss modulus , and calculate the loss factor The control loss factor ranges from 0.2 to 0.4;

[0024] S35. After the dynamic cross-linking reaction is completed, the cross-linked composite material is slowly cooled to room temperature, and the cooled material is calendered using calendering equipment, with the calendered thickness controlled to be 50 - 80 microns;

[0025] S36. The surface roughness of the sheet is detected to ensure that the roughness is less than 0.2 microns. At the same time, dynamic thermomechanical analysis is carried out to test the storage modulus and weather resistance of the material, and an ultraviolet aging experiment is carried out to verify the ultraviolet shielding and photocatalytic stability of the surface functional material, and finally the surface functional material is obtained.

[0026] Optionally, the specific steps of S4 include:

[0027] S41. The obtained surface functional material is placed in an extruder to prepare the surface functional material. The temperature is set to 180°C - 200°C, and the screw rotation speed is set to 60 rpm - 80 rpm at the same time, so that the material is fully plasticized and extruded into a uniform sheet, with the thickness controlled to be 50 - 100 microns;

[0028] S42. The nanofiber-reinforced composite material is placed in a twin-screw extruder to prepare the intermediate layer reinforcing material. The feeding rate is adjusted to 5 - 10 kg / h, the temperature is set to 200°C - 220°C, the screw rotation speed is 100 rpm - 150 rpm, and continuous fiber reinforcing phases are added to make the material form a shell-like structure, and an extruded reinforcing material sheet with a thickness of 2 mm - 3 mm is formed;

[0029] S43. The conductive polythiophene composite material and the flexible filler are mixed at a mass ratio of 9:1 and then placed in a single-screw extruder to prepare the bottom conductive material. The temperature is set to 160°C - 180°C through a temperature control system, the screw rotation speed is adjusted to 50 rpm - 70 rpm, and a thermoplastic forming process is used to extrude into a sheet with a thickness of 100 - 150 microns;

[0030] S44. The surface functional material, the intermediate layer reinforcing material, and the bottom conductive material are sequentially added to a dynamic rotating twin-screw extruder. The screw rotation speed is adjusted to 100 rpm - 120 rpm, the feeding order is set as the bottom material to the intermediate layer material and then to the surface material, and the temperature gradient is controlled to gradually increase from 180°C at the bottom to 220°C at the surface;

[0031] S45. The multi-layer structural material extruded from the extruder is cooled by a cooling roll. The temperature of the cooling roll is set to 10°C - 20°C, and the pressure between the rolls is adjusted to 1 MPa - 2 MPa. The thickness of the sheet is controlled by a multi-stage roll pressing and cooling system;

[0032] S46. Finally, a multi-layer structural substrate is formed, and the cooled multi-layer structural material is subjected to dynamic mechanical property testing, with a flexural modulus greater than 80 MPa.

[0033] Optionally, the specific steps of S8 include:

[0034] S81. Place the multi-layer co-extruded tile under an ultraviolet light irradiation device, set the light intensity to 30 mW / cm², the irradiation distance to 20 cm, and the duration to 2 hours. Measure the concentration of reactive oxygen generated on the surface of the tile by the iodometric method, and the generated concentration of reactive oxygen is

[0035] above;

[0036] S82. Catalyze on the surface of the tile in an ultraviolet light irradiation environment for 1 hour, collect the degraded solution, and measure the change in transmittance using an ultraviolet spectrophotometer:

[0037] ;

[0038] Among them, represents the degradation efficiency, represents the initial pollutant concentration, represents the pollutant concentration after degradation;

[0039] S83. Apply a constant voltage to the conductive polythiophene composite layer at the bottom of the tile, and monitor the resistance value . When the resistance change rate exceeds 5%, mark it as the crack occurrence point;

[0040] S84. Use the embedded intelligent monitoring module to record the resistance change trend of the conductive polythiophene composite layer in real time. The intelligent monitoring module sets an alarm mechanism and records the aging crack propagation curve;

[0041] S85. Apply an alternating stress to the surface of the tile to simulate the dynamic process of crack propagation under environmental conditions. Set the alternating stress parameters as a frequency of 5 Hz, an amplitude of 2 MPa. After continuous stress action for 2 hours, record the crack propagation length to complete crack detection and real-time perception of the aging state.

[0042] Optionally, the specific steps of S84 include:

[0043] S841. Based on the initial resistance of the conductive polythiophene composite layer, measure the relationship between the resistance change rate and the crack propagation length during the crack propagation process through experiments, and establish a dynamic crack propagation model:

[0044] ;

[0045] Among them, represents the real-time resistance of the conductive polythiophene composite layer after crack propagation, Represents the initial resistance of the conductive polythiophene composite layer, Represents the sensitivity coefficient of crack propagation, Represents the non - linear factor of crack propagation, Represents the crack propagation length;

[0046] S842. The resistance value and the resistance change rate are collected in real - time at a sampling frequency of 100 times per second through the resistance sensor embedded in the bottom layer of the tile, and a time - series data stream is formed by combining with the timestamp record;

[0047] S843. The multi - layer state classification of the resistance change rate is carried out by using the support vector machine classification algorithm:

[0048] ;

[0049] Among them, Represents the radial basis kernel function, Represents the feature vector Sample point, Represents the feature vector Sample point, Represents the exponential function, Represents the kernel width parameter;

[0050] S844. Based on Gaussian process regression and improved variational Bayesian inference, crack propagation prediction is carried out, a Gaussian process model is established, and a resistance change curve is generated:

[0051] ;

[0052] Among them, Represents the probability distribution of the resistance change rate, Represents the crack propagation length, Represents the resistance change amount caused by crack propagation, Represents the normal distribution, Represents the mean value of the resistance change rate corresponding to crack propagation, Represents the variance of the resistance change rate corresponding to crack propagation;

[0053] The improved variational Bayesian inference is used to optimize the update of the crack propagation posterior distribution:

[0054] ;

[0055] Among them, Represents the time The posterior distribution of the crack propagation length at time Represents the time The predicted distribution of the resistance change rate at time Represents the prior distribution of the crack length at time ;

[0056] Output the predicted value of the future crack propagation length and the confidence interval ;

[0057] S845. Combine the resistance change curve and the predicted crack propagation length, use the long short-term memory network to predict the trend of the crack aging state, and record the aging crack propagation curve;

[0058] S846. According to the crack propagation prediction result and trend analysis, the intelligent monitoring module sets three-level alarm thresholds, including:

[0059] The first-level alarm, the predicted value of the crack propagation in the next 5 hours ;

[0060] The second-level alarm, the predicted value of the crack propagation in the next 3 hours ;

[0061] The third-level alarm, the predicted value of the crack propagation in the next 1 hour .

[0062] An anti-corrosion and highly weather-resistant alloy resin tile according to an embodiment of the present invention is composed of a surface functional layer, an intermediate layer and a bottom layer, and specifically includes: the surface functional layer is made of a dynamically crosslinked fluorosilicon-based polymer, with a thickness of 50-100 microns, containing vanadium oxide and zinc oxide nanoparticles, and has ultraviolet shielding, self-cleaning and photocatalytic degradation functions; the surface is treated with a fluorinated graphene coating and has superhydrophobic properties, and the water droplet contact angle is greater than 160°;

[0063] The intermediate reinforcement layer is composed of a nanofiber-reinforced composite material, with a thickness of 2 mm - 3 mm, designed with a shell-like structure, and has high impact resistance and mechanical properties with a flexural modulus greater than 80 MPa;

[0064] The bottom layer is made of a mixture of a conductive polythiophene composite material and a flexible filler, with a thickness of 100-150 microns, and has the functions of crack detection and aging state monitoring, and real-time data analysis and early warning are carried out through the embedded intelligent monitoring module;

[0065] The surface layer, the intermediate layer and the bottom layer are combined by ultrasonic activation bonding technology and integrally formed by a three-die co-extrusion process.

[0066] The beneficial effects of the present invention are:

[0067] First, the present invention uses a bio-based polymer material based on polyethylene furanoate (PEF) to replace traditional petrochemical-based resins, achieving the renewability and environmental friendliness of the material source. The PEF material not only has excellent mechanical properties and chemical stability, but also greatly improves the weather resistance and anti-corrosion properties of the tile by combining with modified potassium titanate whiskers and composite nanoparticles. Compared with the rapid deterioration of traditional materials under ultraviolet radiation and extreme climate conditions, the tiles of the present invention can still maintain a color stability of more than 95% after 4000 hours of ultraviolet aging test, significantly improving the service life and long-term reliability of the material.

[0068] In addition, the present invention develops a surface functional material with flexibility and self-healing ability by introducing a dynamically crosslinked fluorosilane-based polymer. The dynamic crosslinking technology forms a stable network structure on the surface of the tile, which not only enhances the anti-cracking performance of the material, but also effectively inhibits the propagation of microcracks through the self-healing mechanism. In addition, the vanadium oxide and zinc oxide nanoparticles added to the surface layer material not only provide excellent ultraviolet shielding ability, but also endow the tile surface with photocatalytic degradation function. Combining the superhydrophobic properties of the fluorinated graphene coating, the tile surface exhibits excellent self-cleaning performance, effectively avoiding the accumulation of dust, pollutants and biological attachments, and greatly reducing the maintenance cost.

[0069] The middle layer uses a nanofiber-reinforced composite material, and through the design of a layered structure imitating the shell, it provides excellent impact resistance and toughness, significantly improving the mechanical properties of the tile. Compared with the defect that traditional tiles are easily broken under wind load and physical impact, the tiles of the present invention have significantly improved bending modulus and impact strength, and can better cope with harsh natural conditions. The bottom conductive polythiophene composite material combines an embedded intelligent monitoring module to realize real-time perception of crack detection and aging status. Through a high-precision resistance sensor and an improved variational Bayesian inference algorithm, the present invention can accurately predict the propagation trend of cracks and provide timely maintenance suggestions for users through a three-level alarm mechanism. This intelligent functional design fills the gap in the field of structural health monitoring of existing resin tiles and provides an important guarantee for the long-term safety of buildings.

[0070] In terms of process, the present invention uses a three-die co-extrusion technology to realize the synchronous molding of the surface layer, middle layer and bottom layer materials, and enhances the bonding force of the multi-layer structure through ultrasonic activation bonding technology. Compared with traditional multi-processing or spraying processes, the process flow of the present invention is more efficient, while ensuring the consistency of material properties and the stability of interlayer bonding. The surface functional layer forms a superhydrophobic coating through plasma-enhanced chemical vapor deposition technology. Compared with traditional spraying technology, the coating prepared by this process is more uniform and has significantly improved durability. In addition, the present invention does not use solvents during the entire processing process, avoiding environmental pollution problems and conforming to the concept of green manufacturing. Description of the Drawings

[0071] The drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation to the present invention. In the drawings:

[0072] Figure 1 is the overall flowchart of a preparation process of an anti-corrosion and highly weather-resistant alloy resin tile proposed by the present invention;

[0073] Figure 2 is the structural schematic diagram of a preparation process of an anti-corrosion and highly weather-resistant alloy resin tile proposed by the present invention. Detailed Description of the Invention

[0074] Now, the present invention will be further described in detail with reference to the drawings. These drawings are all simplified schematic diagrams, only showing the basic structure of the present invention in a schematic way, so they only show the components related to the present invention.

[0075] Reference Figure 1 , a preparation process of an anti-corrosion and highly weather-resistant alloy resin tile, includes the following steps:

[0076] S1. Mix polyethylene furandicarboxylate with a toughening agent and an ultraviolet absorber, form a matrix material through melt processing, and uniformly add modified potassium titanate whiskers with surface-grafted fluorine groups into the matrix material by using ultrasonic dispersion technology to prepare a basic composite material;

[0077] S2. Add vanadium oxide and zinc oxide composite nanoparticles prepared by the sol-gel method to the basic composite material, and perform surface modification on the composite nanoparticles to prepare a composite material with ultraviolet shielding and photocatalytic functions;

[0078] S3. Introduce a dynamic crosslinked fluorosilicon-based polymer into the composite material with ultraviolet shielding and photocatalytic functions, and prepare a surface functional material through dynamic crosslinking technology;

[0079] S4. Reshape the surface functional material, the intermediate layer nanofiber-reinforced composite material, and the bottom conductive polythiophene-based composite material respectively, and achieve uniform mixing of multiple components and molecular chain orientation through a dynamic rotating twin-screw extruder to form a multi-layer structured substrate;

[0080] S5. Complete the synchronous co-extrusion molding of the surface layer, the intermediate layer, and the bottom layer through three-die extrusion technology to prepare a multi-layer co-extruded tile;

[0081] S6. Enhance the interfacial bonding strength of the multi-layer co-extruded tile by using ultrasonic activation bonding technology;

[0082] S7. Deposit a fluorinated graphene nanofilm on the surface of the multi-layer co-extruded tile using plasma-enhanced chemical vapor deposition technology to form a superhydrophobic functional layer;

[0083] S8. Conduct a UV photocatalytic function test on the multi-layer co-extruded tile to verify the ability of the surface nanoparticles to generate reactive oxygen species, and combine an intelligent monitoring module through the conductive polythiophene composite layer embedded in the bottom layer to complete crack detection and real-time perception of the aging state.

[0084] In this embodiment, the specific steps of S3 are as follows:

[0085] S31. Place the prepared composite material with UV shielding and photocatalytic functions in a reaction kettle, add a dynamic cross-linked fluorosilicon-based polymer according to 15%-30% of the total mass of the composite material, start the stirring device of the reaction kettle, raise the temperature to 140°C, control the stirring speed at 200 rpm, and maintain the stirring time for 30 minutes;

[0086] S32. Add an initiator and an inhibitor during the mixing process. The initiator is benzoyl peroxide, and the dosage is 0.2% of the total mass of the composite material; the inhibitor is hydroquinone, and the dosage is 0.1% of the total mass of the composite material. Continuously stir to cause a preliminary cross-linking reaction of the fluorosilicon-based polymer;

[0087] S33. Connect a dynamic stress loading device to the reaction kettle, apply a shear rate and shear stress , and set the dynamic stress frequency at 15 Hz, and continuously act for 2 hours to promote the formation of a cross-linked network of the fluorosilicon-based polymer;

[0088] S34. Real-time detect the dynamic mechanical properties of the composite material during the dynamic cross-linking process, monitor the storage modulus and loss modulus , calculate the loss factor , and control the loss factor range at 0.2 - 0.4;

[0089] S35. After the dynamic cross-linking reaction is completed, slowly cool the cross-linked composite material to room temperature, and perform calendering treatment on the cooled material using calendering equipment, and control the calendering thickness at 50 - 80 microns;

[0090] S36. Detect the surface roughness of the sheet to ensure that the roughness is less than 0.2 microns. At the same time, conduct dynamic thermomechanical analysis to test the storage modulus and weather resistance of the material, and conduct a UV aging experiment to verify the UV shielding and photocatalytic stability of the surface functional material, and finally obtain the surface functional material.

[0091] In this embodiment, the specific steps of S4 are as follows:

[0092] S41. Place the obtained surface functional material in an extruder to prepare the surface functional material. Set the temperature to 180°C - 200°C, and at the same time set the screw speed to 60 rpm - 80 rpm to fully plasticize the material and extrude it into a uniform sheet, controlling the thickness to be 50 - 100 microns;

[0093] S42. Place the nanofiber-reinforced composite material in a twin-screw extruder to prepare the intermediate layer reinforcing material. Adjust the feeding rate to 5 - 10 kg / h, set the temperature to 200°C - 220°C, and the screw speed to 100 rpm - 150 rpm. Add the continuous fiber reinforcing phase to make the material form a shell-like layered structure, and extrude it to form a reinforcing material sheet with a thickness of 2 mm - 3 mm;

[0094] S43. Mix the conductive polythiophene composite material and the flexible filler in a mass ratio of 9:1 and place them in a single-screw extruder to prepare the bottom conductive material. Set the temperature to 160°C - 180°C through the temperature control system, adjust the screw speed to 50 rpm - 70 rpm, and use the thermoplastic forming process to extrude it into a sheet with a thickness of 100 - 150 microns;

[0095] S44. Add the surface functional material, the intermediate layer reinforcing material, and the bottom conductive material to the dynamic rotating twin-screw extruder in sequence. Adjust the screw rotation speed to 100 rpm - 120 rpm, set the feeding order to be from the bottom material to the intermediate layer material and then to the surface material, and control the temperature gradient to gradually increase from 180°C at the bottom to 220°C at the surface;

[0096] S45. Cool the multi-layer structure material extruded from the extruder through a cooling roller. Set the temperature of the cooling roller to 10°C - 20°C, and adjust the pressure between the rollers to 1 MPa - 2 MPa, and control the sheet thickness through a multi-stage roller pressing and cooling system;

[0097] S46. Finally, form a multi-layer structure substrate and conduct a dynamic mechanical property test on the cooled multi-layer structure material, with the flexural modulus greater than 80 MPa.

[0098] In this embodiment, the specific content of S8 is as follows:

[0099] S81. Place the multi-layer co-extruded tile under an ultraviolet light irradiation device. Set the light intensity to 30 mW / cm², the irradiation distance to 20 cm, and the duration to 2 hours. Determine the concentration of reactive oxygen generated on the surface of the tile by the iodometric method, and the generated concentration of reactive oxygen is above;

[0100] S82. Catalyze on the surface of the tile in an ultraviolet light irradiation environment for 1 hour, collect the degraded solution, and measure the change in transmittance using an ultraviolet spectrophotometer:

[0101] ;

[0102] Among them, represents the degradation efficiency, represents the initial pollutant concentration, represents the pollutant concentration after degradation;

[0103] S83. Apply a constant voltage to the conductive polythiophene composite layer at the bottom of the tile , and monitor the resistance value . When the resistance change rate exceeds 5%, mark it as the crack occurrence point;

[0104] S84. Use the embedded intelligent monitoring module to record the resistance change trend of the conductive polythiophene composite layer in real time. The intelligent monitoring module sets an alarm mechanism and records the aging crack propagation curve;

[0105] S85. Apply an alternating stress to the surface of the tile to simulate the dynamic process of crack propagation under environmental conditions. Set the alternating stress parameters as a frequency of 5 Hz, an amplitude of 2 MPa, and record the crack propagation length after 2 hours of continuous stress action to complete crack detection and real-time perception of the aging state.

[0106] In this embodiment, the S84 specifically includes:

[0107] S841. Based on the initial resistance of the conductive polythiophene composite layer, measure the relationship between the resistance change rate and the crack propagation length during crack propagation through experiments, and establish a crack propagation dynamic model:

[0108] ;

[0109] Among them, represents the real-time resistance of the conductive polythiophene composite layer after crack propagation, represents the initial resistance of the conductive polythiophene composite layer, represents the sensitivity coefficient of crack propagation, represents the non-linear factor of crack propagation, represents the crack propagation length;

[0110] S842. Through the resistance sensor embedded in the bottom layer of the tile, collect the resistance value and the resistance change rate in real time at a sampling frequency of 100 times per second, and record them in combination with the time stamp to form a time series data stream;

[0111] S843. Use the support vector machine classification algorithm to perform multi-layer state classification on the resistance change rate:

[0112] ;

[0113] Among them, represents the radial basis kernel function, Denote the feature vector Sample point Denote the feature vector Sample point Denote the exponential function Denote the kernel width parameter

[0114] S844. Predict crack growth based on Gaussian process regression and improved variational Bayesian inference, establish a Gaussian process model, and generate a resistance change curve

[0115] ;

[0116] Among them Denote the probability distribution of the resistance change rate Denote the crack growth length Denote the resistance change amount caused by crack growth Denote the normal distribution Denote the mean value of the resistance change rate corresponding to crack growth Denote the variance of the resistance change rate corresponding to crack growth

[0117] Optimize the update of the crack growth posterior distribution using improved variational Bayesian inference ;

[0118] Among them Denote time The posterior distribution of the crack growth length at time Denote time The predicted distribution of the resistance change rate at time Denote the prior distribution of the crack length at time ;

[0119] Output the predicted value of the future crack growth length And the confidence interval ;

[0120] S845. Combine the resistance change curve and the predicted crack growth length, use a long short-term memory network to predict the trend of the crack aging state, and record the aging crack growth curve

[0121] S846. According to the crack growth prediction results and trend analysis, the intelligent monitoring module sets three-level alarm thresholds, including

[0122] Level 1 alarm, the predicted value of crack growth in the next 5 hours ;

[0123] Level 2 alarm, the predicted value of crack growth in the next 3 hours ;

[0124] Level 3 alarm, the predicted value of crack growth in the next 1 hour .

[0125] Reference Figure 2 , an anti-corrosion and highly weather-resistant alloy resin tile, which is composed of a surface functional layer, an intermediate layer and a bottom layer, specifically including: the surface functional layer is made of a dynamically cross-linked fluorosilicon-based polymer, with a thickness of 50-100 microns, containing vanadium oxide and zinc oxide nanoparticles, and has ultraviolet shielding, self-cleaning and photocatalytic degradation functions; the surface is treated with a fluorinated graphene coating, with superhydrophobic properties, and the water droplet contact angle is greater than 160°;

[0126] The intermediate reinforcing layer is composed of a nanofiber-reinforced composite material, with a thickness of 2mm-3mm, designed with a shell-like structure, and has high impact resistance and mechanical properties with a flexural modulus greater than 80 MPa;

[0127] The bottom layer is made of a conductive polythiophene composite material mixed with a flexible filler, with a thickness of 100-150 microns, and has the functions of crack detection and aging state monitoring, and real-time data analysis and early warning are carried out through the embedded intelligent monitoring module;

[0128] The said surface layer, intermediate layer and bottom layer are combined by ultrasonic activation bonding technology and integrally formed by a three-die co-extrusion process. Example 1

[0129] A preparation method of an anti-corrosion and highly weather-resistant alloy resin tile, including the following steps:

[0130] (1) Mix polyethylene furandicarboxylate (PEF), polyetheramide elastomer toughener and ultraviolet absorber in a mass ratio of 70:20:10, and form a matrix material by melt blending at 240°C. Add modified potassium titanate whiskers grafted with fluorine groups on the surface at 12% of the mass of the matrix material, and use ultrasonic dispersion technology to treat for 25 minutes to make the modified potassium titanate whiskers uniformly dispersed in the matrix material to obtain a basic composite material.

[0131] (2) Prepare composite nanoparticles of vanadium oxide and zinc oxide (ZnO) by the sol-gel method in a mass ratio of 1:1. After surface modification of the composite nanoparticles with a silane coupling agent, add them to the basic composite material at a ratio of 5%. Stir at 180°C for 1 hour to obtain a composite material with ultraviolet shielding and photocatalytic functions. (2) Prepare composite nanoparticles of vanadium oxide and zinc oxide (ZnO) by the sol-gel method in a mass ratio of 1:1. After surface modification of the composite nanoparticles with a silane coupling agent, add them to the basic composite material at a ratio of 5%. Stir at 180°C for 1 hour to obtain a composite material with ultraviolet shielding and photocatalytic functions.

[0132] (3) Place the above composite material in a closed reaction kettle, add a dynamic cross-linked fluorosilicon-based polymer at 20% of the total mass of the composite material, and simultaneously add 0.2% benzoyl peroxide (initiator) and 0.1% hydroquinone (polymerization inhibitor). Stir at 200 rpm for 30 minutes at 140 °C. Connect a dynamic stress loading device and apply a shear stress of 15 Hz for 2 hours to promote the formation of a cross-linked network of the fluorosilicon-based polymer. After cooling to room temperature, roll the material into a thin sheet with a thickness of 60 microns to obtain the surface functional material.

[0133] (4) The middle reinforcing layer uses a nanofiber-reinforced composite material, which is prepared according to the design of the laminated structure of a shell, with a thickness of 2.5 mm; the bottom conductive material is made by mixing a conductive polythiophene composite material and a flexible filler in a mass ratio of 9:1 and then thermoplastically forming at 180 °C into a sheet with a thickness of 120 microns. Add the surface functional material, the middle reinforcing layer, and the bottom conductive material to a three-die extruder in sequence, set the temperatures of the bottom layer, the middle layer, and the surface layer to 180 °C, 200 °C, and 220 °C respectively, extrude synchronously and cool through a cooling roller to form a multi-layer structured substrate.

[0134] (5) Use plasma-enhanced chemical vapor deposition technology (PECVD) to deposit a fluorinated graphene coating on the surface of the substrate. The mixed gas is and with a flow ratio of 1:1, a treatment temperature of 120 °C, and a treatment time of 15 minutes to form a superhydrophobic surface layer with a surface contact angle reaching 165°.

[0135] (6) Conduct ultraviolet aging and salt spray tests on the multi-layer tiles. The ultraviolet light aging test is carried out at an intensity of 30 mW / cm² for 4000 hours, and the color retention rate is 96%; there is no obvious corrosion after the salt spray test (5% NaCl, 1000 hours). The photocatalytic performance test shows that the active oxygen concentration of the tiles reaches within 2 hours under ultraviolet light of 30 mW / cm². The crack detection shows that when the resistance change rate of the bottom conductive composite layer exceeds 5%, the intelligent monitoring module can give a real-time alarm and successfully predict the aging trend. Example 2

[0136] A preparation method of an anti-corrosion and highly weather-resistant alloy resin tile, comprising the following steps:

[0137] (1) The preparation of the basic composite material is the same as that in Example 1.

[0138] (2) The preparation of the composite material with ultraviolet shielding and photocatalytic functions is the same as that in Example 1, but the addition amount of the composite nanoparticles is 8% of the mass of the basic composite material.

[0139] (3) Mix the composite material and the dynamically crosslinked fluorosilicon-based polymer at a mass ratio of 85:15, add 0.15% initiator benzoyl peroxide and 0.08% inhibitor hydroquinone, and stir at 130 °C for 40 minutes. Carry out the crosslinking reaction through the dynamic stress action with a shear rate of 10 Hz, and roll it into a sheet with a thickness of 80 microns after cooling.

[0140] (4) Use a twin-screw extruder to prepare the intermediate reinforcing layer nanofiber reinforcing material into a bionic structure sheet with a thickness of 2 mm. Use a single-screw extruder to prepare the bottom conductive material into a sheet with a thickness of 100 microns. Synchronously prepare multi-layer tiles through a three-die extrusion. After cooling, perform multi-stage roll pressing on the tiles to ensure uniform sheet thickness.

[0141] (5) Use the PECVD technology to deposit a fluorinated graphene coating on the surface of the tiles for 12 minutes to form a superhydrophobic layer with a contact angle of 163°.

[0142] (6) Performance tests show that after the tiles are tested under high ultraviolet (4000 hours) and high salt fog (5% NaCl, 1000 hours), the color retention rate reaches 94% and there is no corrosion on the surface. Crack detection is recorded in real time through the change rate of the bottom layer resistance, and the error in predicting the crack propagation length is less than 2%. The finally prepared tiles have excellent weather resistance, corrosion resistance, and intelligent monitoring capabilities.

[0143] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

Claims

1. A process for preparing corrosion-resistant and highly weather-resistant alloy resin tiles, characterized in that: The steps include: S1, mixing polyethylene furandicarboxylate with a toughening agent and an ultraviolet absorber, forming a matrix material by melt processing, and uniformly adding modified potassium titanate whiskers with fluorine-containing groups grafted on the surface into the matrix material by ultrasonic dispersion technology to prepare a basic composite material; S2. preparing composite nanoparticles of vanadium oxide and zinc oxide by a sol-gel method, and adding the composite nanoparticles to a basic composite material after surface modification to prepare a composite material with ultraviolet shielding and photocatalytic functions; S3. Introducing dynamically cross-linked fluorosilicone-based polymers into composite materials with UV shielding and photocatalytic functions, and preparing surface functional materials through dynamic cross-linking technology; S4, preparing and molding the surface functional material, the middle layer nanofiber reinforced composite material and the bottom layer conductive polythiophene-based composite material respectively, and realizing uniform mixing of multiple components and directional arrangement of molecular chains through a dynamic rotating twin-screw extruder to form a multi-layer structure substrate; S5. The surface layer, the middle layer and the bottom layer are co-extruded synchronously by three-die extrusion technology to prepare multi-layer co-extruded tiles; S6. Use ultrasonic activated bonding technology to enhance the interlayer bonding strength of multi-layer co-extruded tiles; S7, depositing a fluorinated graphene nanofilm on the surface of the multi-layer co-extruded tile material using plasma enhanced chemical vapor deposition technology to form a super hydrophobic functional layer; S8. Conduct UV photocatalytic function tests on multi-layer co-extruded tiles to verify the active oxygen generation ability of surface nanoparticles, and complete crack detection and real-time perception of aging status through the conductive polythiophene composite layer embedded in the bottom layer combined with the intelligent monitoring module.

2. The process for preparing a corrosion-resistant and highly weather-resistant alloy resin tile according to claim 1, characterized in that: The S3 specifically includes: S31, placing the prepared composite material with ultraviolet shielding and photocatalytic functions in a reactor, adding a dynamically cross-linked fluorosilicone-based polymer according to 15%-30% of the total mass of the composite material, starting the stirring device of the reactor, raising the temperature to 140° C., controlling the stirring speed to 200 rpm, and maintaining the stirring time for 30 minutes; S32, adding an initiator and an inhibitor during the mixing process, wherein the initiator is benzoyl peroxide, and the amount used is 0.2% of the total mass of the composite material; the inhibitor is hydroquinone, and the amount used is 0.1% of the total mass of the composite material, and continuously stirring to allow the fluorosilicone-based polymer to undergo a preliminary cross-linking reaction; S33, connect the dynamic stress loading device to the reactor, and apply a shear rate of γ = 25s through the device -1 and shear stress τ = 3 MPa, and the dynamic stress frequency is set to 15 Hz, and the action lasts for 2 hours to promote the formation of a cross-linked network of the fluorosilicone-based polymer; S34, real-time detection of dynamic mechanical properties of composite materials during dynamic crosslinking, monitoring of storage modulus E ′ and loss modulus E ″ , calculate the loss factor tanδ = E ″ / E ′ , control the loss factor range to 0.2-0.4; S35, after the dynamic cross-linking reaction is completed, the cross-linked composite material is slowly cooled to room temperature, and the cooled material is calendered using a calendering device to control the calendering thickness to be 50-80 microns; S36. Conduct surface roughness test on the sheet to ensure that the roughness is less than 0.2 microns. Perform dynamic thermomechanical analysis to test the storage modulus and weather resistance of the material, and conduct UV aging experiments to verify the UV shielding and photocatalytic stability of the surface functional material, and finally obtain the surface functional material.

3. The process for preparing a corrosion-resistant and highly weather-resistant alloy resin tile according to claim 1, characterized in that: The S4 specifically includes: S41, placing the obtained surface functional material in an extruder to prepare a surface functional material, setting the temperature to 180°C-200°C, and setting the screw speed to 60rpm-80rpm, so that the material is fully plasticized and extruded into a uniform sheet, and the thickness is controlled to be 50-100 microns; S42, placing the nanofiber reinforced composite material in a twin-screw extruder to prepare an intermediate layer reinforcement material, adjusting the feed rate to 5-10 kg / h, setting the temperature to 200° C.-220° C., and the screw speed to 100 rpm-150 rpm, adding a continuous fiber reinforcement phase to form a shell-like layered structure, and forming a reinforcement material sheet with a thickness of 2 mm-3 mm by extrusion; S43, mixing the conductive polythiophene composite material and the flexible filler in a mass ratio of 9:1 and placing the mixture in a single screw extruder to prepare a bottom conductive material, setting the temperature to 160° C.-180° C. through a temperature control system, adjusting the screw speed to 50 rpm-70 rpm, and extruding the mixture into a sheet with a thickness of 100-150 μm by a thermoplastic molding process; S44, adding the surface layer functional material, the middle layer reinforcing material and the bottom layer conductive material into the dynamic rotating twin-screw extruder in sequence, adjusting the screw rotation speed to 100rpm-120rpm, setting the feeding order to the bottom layer material, the middle layer material and then the surface layer material, and controlling the temperature gradient to gradually increase from 180°C of the bottom layer to 220°C of the surface layer; S45, cooling the multilayer structure material extruded from the extruder through a cooling roller, setting the cooling roller temperature to 10°C-20°C, adjusting the inter-roller pressure to 1MPa-2MPa, and controlling the sheet thickness through a multi-stage roller cooling system; S46. Finally, a multilayer structure substrate is formed and the cooled multilayer structure material is subjected to a dynamic mechanical property test, and the bending modulus is greater than 80 MPa.

4. The process for preparing a corrosion-resistant and highly weather-resistant alloy resin tile according to claim 1, characterized in that: The S8 specifically includes: S81. Place the multi-layer co-extruded tile material under a UV irradiation device with the light intensity set to 30mW / cm 2 The irradiation distance was 20 cm and the duration was 2 hours. The active oxygen concentration generated on the tile surface was measured by iodine titration. The active oxygen concentration was 1.5×10 -5 mol / L or above; S82. Catalyze the tile surface under ultraviolet light for 1 hour, collect the degraded solution, and measure the transmittance change using an ultraviolet spectrophotometer: Among them, E represents the degradation efficiency, C0 represents the initial pollutant concentration, and C represents the pollutant concentration after degradation; S83, applying a constant voltage U=5V to the conductive polythiophene composite layer at the bottom of the tile material, monitoring the resistance value R, and marking it as a crack occurrence point when the resistance change rate exceeds 5%; S84, using the embedded intelligent monitoring module to record the resistance change trend of the conductive polythiophene composite layer in real time, the intelligent monitoring module sets an alarm mechanism, and records the aging crack growth curve; S85. Apply alternating stress to the tile surface to simulate the dynamic process of crack extension under environmental conditions. Set the alternating stress parameters to a frequency of 5 Hz and an amplitude of 2 MPa. Record the crack extension length after 2 hours of continuous stress to complete crack detection and real-time perception of aging status.

5. The process for preparing a corrosion-resistant and highly weather-resistant alloy resin tile according to claim 4, characterized in that: The S84 specifically includes: S841. Based on the initial resistance of the conductive polythiophene composite layer, the relationship between the resistance change rate and the crack extension length during crack extension was measured experimentally to establish a dynamic crack extension model: R=R0(1+k·e β·ΔL ): Wherein, R represents the real-time resistance of the conductive polythiophene composite layer after crack extension, R0 represents the initial resistance of the conductive polythiophene composite layer, k represents the sensitivity coefficient of crack extension, β represents the nonlinear factor of crack extension, and ΔL represents the crack extension length; S842, using a resistance sensor embedded in the bottom layer of the tile material, collecting resistance values ​​and resistance change rates in real time at a sampling frequency of 100 times per second, and combining with timestamp records to form a time series data stream; S843, using support vector machine classification algorithm to perform multi-layer state classification of resistance change rate: Among them, K(x i ,x j ) represents the radial basis kernel function, x i represents the feature vector i sample point, x j represents the feature vector j sample point, exp represents the exponential function, and σ represents the kernel width parameter; S844, based on Gaussian process regression and improved variational Bayesian inference, crack propagation prediction is performed, a Gaussian process model is established, and a resistance change curve is generated: P(ΔR|ΔL)~N(μ(ΔL),σ 2 (ΔL)); Where P(ΔR|ΔL) represents the probability distribution of the resistance change rate, ΔL represents the crack extension length, ΔR represents the resistance change caused by crack extension, and N(μ(ΔL),σ 2 (ΔL)) represents the normal distribution, μ(ΔL) represents the mean value of the resistance change rate corresponding to crack extension, σ 2 (ΔL) represents the variance of the resistance change rate corresponding to crack extension; Improved variational Bayesian inference is used to optimize the update of crack extension posterior distribution: P(ΔL t+Δt |ΔL t )∝P(ΔR|ΔL t+Δt )P(ΔL t+Δt |ΔL t ); Among them, P(ΔL t+Δt |L t ) represents the posterior distribution of the crack extension length at time t+Δt, P(ΔR|ΔL t+Δt ) represents the predicted distribution of the resistance change rate at time t+Δt, P(ΔL t+Δt |L t ) represents the prior distribution of crack length at time t+Δt; Output the predicted value of future crack extension length E[ΔL t+Δt ] and confidence interval ±σ(ΔL t+Δt ); S845. Combining the resistance change curve and the predicted crack extension length, the long short-term memory network is used to predict the trend of the crack aging state, and the aging crack extension curve is recorded; S846. According to the crack growth prediction results and trend analysis, the intelligent monitoring module sets three levels of alarm thresholds, including: Level 1 alarm, predicted crack extension value E[ΔL in the next 5 hours t+Δt ]>5mm; Level 2 alarm, predicted crack extension value E[ΔL in the next 3 hours t+Δt ]>10mm; Level 3 alarm, predicted crack extension value E[ΔL t+Δt ]>15mm.

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