AI intelligent digital graphene heating wallboard

Abstract

The invention relates to the technical field of functional building materials, in particular to an AI intelligent digital graphene heating wallboard which is prepared from a modified epoxy resin matrix, a multilayer graphene conductive filler, nano tourmaline powder and a rare earth activator. The preparation method comprises the following steps: carrying out surface grafting treatment on graphene by using a silane coupling agent to construct a conductive network precursor, dispersing nano tourmaline powder and a rare earth activator into a modified epoxy resin matrix under a high shear force field, and inducing filler to be directionally arranged through a gradient heating curing process, and carrying out compression molding to obtain the heating wallboard material. According to the technical scheme, the defects that a traditional heating wallboard is low in electrothermal conversion efficiency and lacks a healthy physical therapy function are effectively overcome, the efficient electrothermal performance of graphene is utilized to excite tourmaline to release far infrared rays with specific wavelengths, resonance absorption of water molecules in human tissues is triggered, and the health of the human tissues is improved. Therefore, the indoor thermal environment comfort is remarkably improved, and the health effect of promoting blood circulation is achieved.

Description

Technical Field

[0001] This invention relates to the field of functional building materials technology, and in particular to an AI intelligent digital graphene heating wall panel. Background Technology

[0002] The field of functional building materials technology relates to an interior wall covering material that integrates decoration, heating, and physiotherapy functions. Among these, traditional graphene heating wall panels with far-infrared functionality refer to panels made by mixing carbon-based conductive particles and common mineral fillers with resin as a binder, through a simple physical blending and molding process. These panels typically utilize the thermal effect of electric current to raise indoor temperatures and provide basic heating services based on the material's own thermal radiation characteristics.

[0003] Existing technologies using metal resistance wires or ordinary carbon crystal powder as heating sources suffer from low energy utilization due to limited electrothermal conversion efficiency. Furthermore, these heating components are prone to localized overheating and safety hazards during long-term operation due to uneven filler distribution. Additionally, the lack of radiation emission sources targeting specific bioactive wavelengths prevents them from generating far-infrared spectra that can effectively activate water molecules in human cells. Moreover, traditional polymer matrices are prone to interfacial stress concentration under frequent thermal cycling conditions, leading to coating peeling and significantly shortening the product's lifespan. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing technologies and propose an AI-powered intelligent digital graphene heating wall panel.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: an AI intelligent digital graphene heating wall panel, wherein the materials used to prepare the AI ​​intelligent digital graphene heating wall panel include: (a) Modified waterborne polyurethane resin matrix, the content of which is 45-60 parts by weight; (b) Silane-based graphene conductive filler, the content of which is 8-15 parts by weight; (c) Rare earth doped tourmaline composite powder, the content of which is 20-30 parts by weight; (d) Interface compatibilizer, the content of which is 2-5 parts by weight.

[0006] As a further aspect of the present invention, the average diameter of the silane-based graphene conductive filler sheets is 5-10 micrometers. The average thickness of the silane-based graphene conductive filler is 1-3 nanometers. The BET specific surface area of ​​silane-based graphene conductive fillers is 250-350 square meters per gram. The surface grafting rate of silane-based graphene conductive fillers is 3.5%-5.0%.

[0007] As a further aspect of the present invention, the median particle size D50 of the rare earth-doped tourmaline composite powder is 0.8-1.5 micrometers; The normal total emissivity of rare earth-doped tourmaline composite powder in the 8-14 micrometer wavelength range is 0.92-0.96. The mass fraction of rare earth cerium ions in rare earth-doped tourmaline composite powder is 2.5%-4.0%. A method for preparing an AI-powered intelligent digital graphene heating wall panel, the method comprising the following steps: S1: Graphene oxide powder is dispersed in an ethanol aqueous solution, mixed with silane coupling agent KH-560 and the pH value is adjusted to 4.0-5.0. Grafting reaction is carried out under ultrasonic power of 800W to condense the silanol groups generated by silane hydrolysis with the hydroxyl groups on the graphene surface. Silane-based graphene conductive filler is prepared by centrifugation and vacuum drying. S2: Nanoscale tourmaline powder is mixed with cerium nitrate solution for ion adsorption, and then placed in a tube furnace for high-temperature calcination at 600°C under an inert atmosphere to drive cerium ions to occupy the defect sites in the tourmaline crystal lattice. Rare earth-doped tourmaline composite powder is then prepared by air jet milling. S3: The modified waterborne polyurethane resin matrix is ​​pumped into a high-shear emulsifier, and silane-based graphene conductive filler, rare earth-doped tourmaline composite powder and interface compatibilizer are added in sequence. The mixture is dispersed and mixed at a shear rate of 3000 rpm for 30 minutes to make the filler uniformly distributed in the matrix and to construct a heating slurry. S4: Inject the heating slurry into a metal mold preheated to 120°C, and hold it under pressure of 15MPa for 45 minutes to induce the graphene sheets to align along the plane. After demolding and natural cooling, the AI ​​intelligent digital graphene heating wall panel is prepared.

[0008] As a further aspect of the present invention, the preparation process of silane-based graphene conductive filler specifically includes: The BET specific surface area of ​​graphene oxide powder was determined. The theoretical grafting amount of silane coupling agent KH-560 is calculated using the following formula: ; Dissolve the calculated amount of silane coupling agent KH-560 in a mixed solvent of ethanol and water and stir to hydrolyze for 15-20 minutes; Graphene oxide powder was added to the hydrolyzed silane solution and grafted in a constant temperature water bath at 60-70℃ for 4-6 hours. in, This represents the quality of the silane coupling agent KH-560. This represents the quality of graphene oxide powder. The BET specific surface area represents the graphene oxide powder. Represents the minimum coverage area of ​​a single silane molecule. Represents Avogadro's constant. This represents the molar mass of the silane coupling agent KH-560. This represents the excess reaction coefficient.

[0009] As a further aspect of the present invention, the ion adsorption step in the rare earth-doped tourmaline composite powder specifically includes: Prepare a cerium nitrate solution with a molar concentration of 0.1-0.2 mol / L; A suspension system was constructed by adding nano-sized tourmaline powder to a cerium nitrate solution; Adjust the pH of the suspension system to 3.5-4.5; The suspension system was subjected to ultrasonic oscillation treatment at a temperature of 40-50℃ for 1-2 hours to allow cerium ions to be adsorbed into the surface pores of nano-scale tourmaline powder. The suspension system was filtered and dried to obtain the doped precursor powder.

[0010] As a further aspect of the present invention, the high-temperature calcination step in the rare earth-doped tourmaline composite powder specifically includes: The doped precursor powder is placed in an alumina crucible and pushed into the isothermal zone of a tube furnace. High-purity nitrogen gas is introduced into the tubular atmosphere furnace, and the gas flow rate is controlled at 200-300 ml per minute; The furnace temperature is raised to 600℃ at a heating rate of 5-8℃ per minute and held for calcination for 2-3 hours, so that the adsorbed cerium ions diffuse into the tourmaline crystal structure. After the furnace has cooled naturally to room temperature, the calcined product is removed. The calcined products were deagglomerated and dispersed using an air jet mill, with the milling pressure controlled at 0.6-0.8 MPa, to obtain rare earth-doped tourmaline composite powder.

[0011] As a further aspect of the present invention, the steps for constructing the heating slurry specifically include: Start the circulating cooling water system of the high-shear emulsifier and control the material temperature between 25-35℃; Add the modified waterborne polyurethane resin matrix into the dispersion vessel and start low-speed stirring. The silane-based graphene conductive filler was added in three batches, and after each addition, it was pre-dispersed at 1000 rpm for 5-10 minutes. Rare earth-doped tourmaline composite powder and interfacial compatibilizer were added, and the rotation speed was increased to 3000 rpm for high-intensity shear dispersion; During the dispersion process, the dispersion vessel is evacuated to -0.08MPa to -0.09MPa to remove air bubbles from the slurry.

[0012] As a further aspect of the present invention, the curing step of the AI ​​intelligent digital graphene heating wall panel specifically includes: Apply release agent evenly to the inner surface of the metal mold and preheat to 120°C; The degassed heating slurry is quantitatively injected into the cavity of the metal mold; Close the mold and increase the molding pressure to 15MPa at a pressurization rate of 1-2MPa per minute; Maintain a temperature of 120℃ and a pressure of 15MPa for 45 minutes to carry out the cross-linking and curing reaction, so that the resin matrix forms a three-dimensional network structure; Open the mold cooling channel and introduce cooling oil to reduce the mold temperature to below 60°C.

[0013] As a further aspect of the present invention, the preparation method of the AI ​​intelligent digital graphene heating wall panel further includes a post-processing step, wherein the post-processing step includes: Open the metal mold and remove the solidified sheet material; Place the board in a constant temperature forced-air drying oven and perform secondary heat curing at 80℃ for 4-6 hours; The normal total emissivity of the substrate was detected using an infrared spectrometer; The surface sheet resistance of the board is tested using a four-probe tester, and qualified products with a surface sheet resistance in the range of 10-50 ohms are screened.

[0014] Compared with the prior art, the advantages and positive effects of the present invention are as follows: In this invention, a highly efficient conductive percolation network is constructed by surface grafting modification of graphene using a silane coupling agent, which significantly improves the electrothermal conversion efficiency. Nano-tourmaline powder activated by rare earth elements is introduced as a radiation center to emit far-infrared rays that match the inherent frequency of human water molecules when heated, inducing intracellular water molecule resonance absorption to achieve the health therapy function of increasing body oxygen content and restoring cell vitality. Furthermore, high-temperature resistant modified polyurethane is used as a matrix to enhance the interfacial bonding force of the material during thermal expansion and contraction, thereby extending the service life of the graphene heating wall panel material with far-infrared function. Attached Figure Description

[0015] Figure 1 This is a flowchart illustrating the preparation method of an AI-powered intelligent digital graphene heating wall panel according to the present invention. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the technical solutions of this invention and do not constitute a limitation on the scope of protection.

[0017] In the description of this invention, the process flow relationships or material and energy transfer paths indicated by terms such as "unit," "step," "equipment," "pipeline," "material flow," and "process parameters" are defined based on the process flow diagram or equipment structure diagram corresponding to the embodiments. This way of expression is only used to clearly illustrate the logical relationship between the elements in the technical solution, and not to limit the specific equipment connection method or physical layout. The term "multiple" includes two or more technical units, including but not limited to multiple reactors, pumps, valves, separation units, or detection instruments and other expandable elements. The specific number is determined according to specific process requirements or production scale and needs to be specifically stated.

[0018] Example 1 In this embodiment, the raw material ratio for preparing the AI ​​intelligent digital graphene heating wall panel is as follows: 45 parts by weight of modified waterborne polyurethane resin matrix, 8 parts by weight of silanized graphene conductive filler, 20 parts by weight of rare earth-doped tourmaline composite powder, and 2 parts by weight of interface compatibilizer. During the preparation process, the pH value of the silanization treatment is adjusted to 4.0, the hydrolysis time is 15 minutes, the grafting reaction temperature is 60°C, and the grafting reaction time is 4 hours; in the ion adsorption stage, the molar concentration of cerium nitrate solution is 0.1 mol / L, the pH value of the suspension system is 3.5, the ultrasonic adsorption temperature is 40°C, and the adsorption time is 1 hour; in the high-temperature calcination stage, the nitrogen flow rate is 200 ml / min, the heating rate is 5°C / min, the holding time is 2 hours, and the airflow pulverization pressure is 0.6 MPa; the heating slurry dispersion temperature is 25°C, the pre-dispersion time is 5 minutes, and the vacuum degree is -0.08 MPa; in the curing and molding stage, the mold is preheated to 120°C, the pressurization rate is 1 MPa / min, the holding time is 45 minutes, and the secondary heat curing time is 4 hours.

[0019] Please see Figure 1 This invention provides a technical solution: a method for preparing an AI intelligent digital graphene heating wall panel, comprising the following steps: S1: Graphene oxide powder is dispersed in an ethanol aqueous solution, mixed with silane coupling agent KH-560 and the pH value is adjusted to 4.0-5.0. Grafting reaction is carried out under ultrasonic power of 800W to condense the silanol groups generated by silane hydrolysis with the hydroxyl groups on the graphene surface. Silane-based graphene conductive filler is prepared by centrifugation and vacuum drying.

[0020] The preparation process of silane-based graphene conductive filler specifically includes: The BET specific surface area of ​​graphene oxide powder was determined. The theoretical grafting amount of silane coupling agent KH-560 is calculated using the following formula: ; Dissolve the calculated amount of silane coupling agent KH-560 in a mixed solvent of ethanol and water and stir to hydrolyze for 15-20 minutes; Graphene oxide powder was added to the hydrolyzed silane solution and grafted in a constant temperature water bath at 60-70℃ for 4-6 hours. in, This represents the quality of the silane coupling agent KH-560. This represents the quality of graphene oxide powder. The BET specific surface area represents the graphene oxide powder. Represents the minimum coverage area of ​​a single silane molecule. Represents Avogadro's constant. This represents the molar mass of the silane coupling agent KH-560. This represents the excess reaction coefficient.

[0021] The average diameter of the prepared silane-based graphene conductive filler sheets is 5-10 micrometers, and the average thickness is 1-3 nanometers. BET has a specific surface area of ​​250-350 square meters per gram and a surface grafting rate of 3.5%-5.0%.

[0022] 1000g of graphene oxide powder was weighed and fed into a high-speed dispersion vessel containing 50L of ethanol-water solution (ethanol:water volume ratio 9:1) using a powder feeder. The agitator in the dispersion vessel was started and the rotation speed was set to 500 rpm. The ultrasonic generator was turned on and the ultrasonic power was set to 800 watts to perform ultrasonic exfoliation and dispersion treatment on the mixture for 30 minutes. During this period, the graphene oxide powder was tested using a fully automated specific surface area and pore size analyzer, and the BET specific surface area of ​​the graphene oxide powder was measured. The minimum coverage area of ​​a single silane molecule is determined to be 280 square meters per gram. for The molar mass of silane coupling agent KH-560 per square meter It is 236.34 grams per mole, and Avogadro's constant. Pick Per mole. Set the excess reaction coefficient. The value is 3.5. Substitute the above parameters into the formula. In the calculation, the required mass of silane coupling agent KH-560 was determined. It weighs 938.4 grams. Of which, This represents the quality of the silane coupling agent KH-560. This represents the quality of graphene oxide powder. The BET specific surface area represents the graphene oxide powder. Represents the minimum coverage area of ​​a single silane molecule. Represents Avogadro's constant. This represents the molar mass of the silane coupling agent KH-560. The excess coefficient represents the reaction. 938.4 g of silane coupling agent KH-560 was weighed and added to a pre-hydrolysis tank containing 2 liters of ethanol aqueous solution. A magnetic stirrer was turned on, and the speed was adjusted to 200 rpm. Hydrolysis was carried out at room temperature for 15 minutes. The hydrolyzed silane solution was added dropwise to the graphene oxide dispersion using a peristaltic pump. After the addition was complete, the pH of the system was adjusted to 4.0 by titration with glacial acetic acid. A constant-temperature water bath circulation system was turned on, and the water bath temperature was set to 60℃. The temperature was maintained constant, and the grafting reaction was carried out for 4 hours under the combined action of mechanical stirring at 300 rpm and ultrasonic assistance. After the reaction, the product slurry was pumped into a high-speed centrifuge and centrifuged at 8000 rpm for 15 minutes. The supernatant was discarded. The precipitate was washed three times with anhydrous ethanol and placed in a vacuum drying oven. It was dried at 60℃ and -0.1 MPa for 12 hours to obtain the silane-based graphene conductive filler. Testing revealed that the average diameter of the silane-based graphene conductive filler sheets was 5 micrometers, the average thickness was 1 nanometer, the BET specific surface area was 250 square meters per gram, and the surface grafting rate was 3.5%.

[0023] The aforementioned silane coupling agent KH-560 refers to γ-(2,3-epoxypropoxy)propyltrimethoxysilane, a silane coupling agent containing epoxy groups, which is often used to improve the bonding force between inorganic materials and organic polymer materials.

[0024] S2: Nanoscale tourmaline powder is mixed with cerium nitrate solution for ion adsorption, and then placed in a tube furnace for high-temperature calcination at 600℃ under an inert atmosphere to drive cerium ions to occupy the defect sites in the tourmaline crystal lattice. Rare earth-doped tourmaline composite powder is then prepared by air jet milling.

[0025] The specific steps of ion adsorption in rare earth-doped tourmaline composite powder include: Prepare a cerium nitrate solution with a molar concentration of 0.1-0.2 mol / L; A suspension system was constructed by adding nano-sized tourmaline powder to a cerium nitrate solution; Adjust the pH of the suspension system to 3.5-4.5; The suspension system was subjected to ultrasonic oscillation treatment at a temperature of 40-50℃ for 1-2 hours to allow cerium ions to be adsorbed into the surface pores of nano-scale tourmaline powder. The suspension system was filtered and dried to obtain the doped precursor powder.

[0026] The high-temperature calcination process specifically includes: The doped precursor powder is placed in an alumina crucible and pushed into the isothermal zone of a tube furnace. High-purity nitrogen gas is introduced into the tubular atmosphere furnace, and the gas flow rate is controlled at 200-300 ml per minute; The furnace temperature is raised to 600℃ at a heating rate of 5-8℃ per minute and held for calcination for 2-3 hours, so that the adsorbed cerium ions diffuse into the tourmaline crystal structure. After the furnace has cooled naturally to room temperature, the calcined product is removed. The calcined products were deagglomerated and dispersed using an air jet mill, with the milling pressure controlled at 0.6-0.8 MPa, to obtain rare earth-doped tourmaline composite powder. The median particle size D50 of the prepared rare earth-doped tourmaline composite powder was 0.8-1.5 μm. The normal total emissivity in the 8-14 micrometer band is 0.92-0.96; The mass fraction of rare earth cerium ions is 2.5%-4.0%.

[0027] Deionized water was added to a dissolving vessel, and cerium nitrate crystals were weighed and added to the water. Stirring was started to dissolve the crystals, preparing 20 liters of cerium nitrate solution with a molar concentration of 0.1 mol / L. 5 kg of nano-sized tourmaline powder was weighed and added to the cerium nitrate solution. A disperser was started and stirred at 1500 rpm for 20 minutes. The pH of the suspension was monitored using a precision pH meter, and dilute nitric acid solution was added dropwise to adjust the pH to 3.5. The container containing the suspension was placed in an ultrasonic cleaning tank, and the heating temperature was set to 40℃ and the ultrasonic frequency to 40 kHz for ultrasonic oscillation treatment for 1 hour. The suspension was separated into solid and liquid components using a plate and frame filter press. The filter cake was dried to constant weight in a 105℃ forced-air drying oven to obtain the doped precursor powder. The dried doped precursor powder was loaded into a high-purity corundum crucible, filling it to half its volume. The crucible was then placed in the isothermal zone of a tubular atmosphere furnace. High-purity nitrogen gas was introduced into the furnace at a flow rate of 200 ml / min for 30 minutes. The heating program was then started, with a heating rate of 5°C / min, raising the furnace temperature to 600°C and maintaining this constant temperature for 2 hours. After the program ended, the nitrogen atmosphere was allowed to cool naturally to room temperature with the furnace. The calcined product was removed and fed into a fluidized bed jet mill. The compressed air inlet pressure was set to 0.8 MPa, the grinding chamber working pressure to 0.6 MPa, and the classifier wheel speed to 4000 rpm. Rare earth-doped tourmaline composite powder was collected by a cyclone separator. Testing revealed that the median particle size (D50) of the rare earth-doped tourmaline composite powder was 0.8 μm, the normal total emissivity in the 8-14 μm wavelength range was 0.92, and the doping mass fraction of rare earth cerium ions was 2.5%.

[0028] The aforementioned nano-sized tourmaline powder refers to tourmaline particles with a particle size in the range of 1-100 nanometers. It has piezoelectric and pyroelectric properties and can generate weak currents and release negative ions when heated or compressed.

[0029] S3: The modified waterborne polyurethane resin matrix is ​​pumped into a high-shear emulsifier, and silane-based graphene conductive filler, rare earth-doped tourmaline composite powder and interface compatibilizer are added in sequence. The mixture is then dispersed and mixed at a shear rate of 3000 rpm for 30 minutes to ensure that the filler is evenly distributed in the matrix and to construct a heating slurry.

[0030] The material ratio for preparing the AI ​​intelligent digital graphene heating wall panel is as follows: The modified waterborne polyurethane resin matrix content is 45-60 parts by weight; The content of silane-based graphene conductive filler is 8-15 parts by weight; The rare earth-doped tourmaline composite powder contains 20-30 parts by weight. The interface compatibilizer content is 2-5 parts by weight. The specific steps for constructing the exothermic slurry include: Start the circulating cooling water system of the high-shear emulsifier and control the material temperature between 25-35℃; Add the modified waterborne polyurethane resin matrix into the dispersion vessel and start low-speed stirring. The silane-based graphene conductive filler was added in three batches, and after each addition, it was pre-dispersed at 1000 rpm for 5-10 minutes. Rare earth-doped tourmaline composite powder and interfacial compatibilizer were added, and the rotation speed was increased to 3000 rpm for high-intensity shear dispersion; During the dispersion process, the dispersion vessel is evacuated to -0.08MPa to -0.09MPa to remove air bubbles from the slurry.

[0031] Start the circulating cooling water unit of the high-shear emulsifier, set the cooling water outlet temperature, and control the material temperature in the dispersion vessel to maintain at 25℃. Add 45 kg of modified waterborne polyurethane resin matrix to the dispersion vessel and start the anchor-type agitator for low-speed stirring at 60 rpm. Weigh 8 kg of the silane-based graphene conductive filler prepared in step S1 and divide it into three equal parts. Add the first part of filler, set the emulsifier speed to 1000 rpm, and disperse for 5 minutes; add the second and third parts sequentially, maintaining a speed of 1000 rpm for 5 minutes after each addition. Add 20 kg of rare earth-doped tourmaline composite powder prepared in step S2 and 2 kg of silane-based interface compatibilizer to the dispersion vessel. Increase the emulsifier speed to 3000 rpm and perform shear dispersion for 30 minutes. Simultaneously with the start of dispersion, turn on the vacuum pump to evacuate the inside of the dispersion vessel, and adjust the vacuum regulating valve to stabilize the vacuum level inside the vessel at -0.08 MPa. After dispersion, the vacuum pump is turned off, the vacuum is broken and the pressure is restored to normal, resulting in a homogeneous, defoamed exothermic slurry.

[0032] The aforementioned modified waterborne polyurethane resin matrix refers to a polyurethane aqueous dispersion that has been modified by introducing hydrophilic groups such as carboxyl or sulfonic acid groups and by chain extenders. It has excellent film-forming properties, heat resistance, and mechanical properties.

[0033] S4: Inject the heating slurry into a metal mold preheated to 120°C, and hold it under pressure of 15MPa for 45 minutes to induce the graphene sheets to align along the plane. After demolding and natural cooling, the AI ​​intelligent digital graphene heating wall panel is prepared.

[0034] The curing process specifically includes: Apply release agent evenly to the inner surface of the metal mold and preheat to 120°C; The degassed heating slurry is quantitatively injected into the cavity of the metal mold; Close the mold and increase the molding pressure to 15MPa at a pressurization rate of 1-2MPa per minute; Maintain a temperature of 120℃ and a pressure of 15MPa for 45 minutes to carry out the cross-linking and curing reaction, so that the resin matrix forms a three-dimensional network structure; Open the mold cooling channel and introduce cooling oil to reduce the mold temperature to below 60°C.

[0035] The method also includes a post-processing step, which includes: Open the metal mold and remove the solidified sheet material; Place the board in a constant temperature forced-air drying oven and perform secondary heat curing at 80℃ for 4-6 hours; The normal total emissivity of the substrate was detected using an infrared spectrometer; The surface sheet resistance of the board is tested using a four-probe tester, and qualified products with a surface sheet resistance in the range of 10-50 ohms are screened.

[0036] A stainless steel flat mold with an inner cavity size of 1200 mm × 2400 mm was selected, and a fluorinated water-based release agent was sprayed onto the inner surface of the mold. The mold heating oil temperature controller was turned on, and the heat transfer oil temperature was set. Heating was achieved through the internal flow channels of the mold, stabilizing the inner surface temperature at 120°C. The heating slurry prepared in step S3 was injected into the mold cavity via a metering pump. The mold cover was closed. The hydraulic press mold closing system was started. The pressurization program was set to a pressure increase rate of 1 MPa per minute, allowing the molding pressure to rise to 15 MPa within 15 minutes. The mold temperature was maintained at 120°C and the pressure at 15 MPa for constant temperature and pressure curing for 45 minutes. After the curing process, 20°C cooling oil was introduced to lower the mold temperature. When the mold temperature dropped below 60°C, the hydraulic press was depressurized, the mold was opened, and the cured AI intelligent digital graphene heating wall panel semi-finished product was removed.

[0037] The demolded boards were placed in a constant-temperature forced-air drying oven. The oven temperature was set to 80℃ for a second heat curing process of 4 hours. After curing, the boards were allowed to cool naturally to room temperature. The normal total emissivity of the board samples was measured using a Fourier transform infrared spectroscopy (FTIR) instrument. Nine evenly distributed test points were selected on the board surface, and the surface sheet resistance was measured using a four-probe resistance meter.

[0038] Table 1. Experimental Test Results of Example 1 ; Table 1 presents the specific test data for the AI ​​intelligent digital graphene heating wall panel prepared in Example 1.

[0039] Table 2 Comparison of Product Performance in Example 1 ; Table 2 shows a comparison of the key performance indicators between the product of Example 1 and existing conventional carbon crystal heating plates.

[0040] Example 2 In this embodiment, the raw material ratio for preparing the AI ​​intelligent digital graphene heating wall panel is as follows: 60 parts by weight of modified waterborne polyurethane resin matrix, 15 parts by weight of silanized graphene conductive filler, 30 parts by weight of rare earth-doped tourmaline composite powder, and 5 parts by weight of interface compatibilizer. During the preparation process, the pH value of the silanization treatment is adjusted to 5.0, the hydrolysis time is 20 minutes, the grafting reaction temperature is 70°C, and the grafting reaction time is 6 hours; in the ion adsorption stage, the molar concentration of cerium nitrate solution is 0.2 mol / L, the pH value of the suspension system is 4.5, the ultrasonic adsorption temperature is 50°C, and the adsorption time is 2 hours; in the high-temperature calcination stage, the nitrogen flow rate is 300 ml / min, the heating rate is 8°C / min, the holding time is 3 hours, and the airflow pulverization pressure is 0.8 MPa; the heating slurry dispersion temperature is 35°C, the pre-dispersion time is 10 minutes, and the vacuum degree is -0.09 MPa; in the curing and molding stage, the mold is preheated to 120°C, the pressurization rate is 2 MPa / min, the holding time is 45 minutes, and the secondary heat curing time is 6 hours.

[0041] Please see Figure 1 This invention provides a technical solution: a method for preparing an AI intelligent digital graphene heating wall panel, comprising the following steps: S1: Graphene oxide powder is dispersed in an ethanol aqueous solution, mixed with silane coupling agent KH-560 and the pH value is adjusted to 4.0-5.0. Grafting reaction is carried out under ultrasonic power of 800W to condense the silanol groups generated by silane hydrolysis with the hydroxyl groups on the graphene surface. Silane-based graphene conductive filler is prepared by centrifugation and vacuum drying.

[0042] The preparation process of silane-based graphene conductive filler specifically includes: The BET specific surface area of ​​graphene oxide powder was determined. The theoretical grafting amount of silane coupling agent KH-560 is calculated using the following formula: ; Dissolve the calculated amount of silane coupling agent KH-560 in a mixed solvent of ethanol and water and stir to hydrolyze for 15-20 minutes; Graphene oxide powder was added to the hydrolyzed silane solution and grafted in a constant temperature water bath at 60-70℃ for 4-6 hours. in, This represents the quality of the silane coupling agent KH-560. This represents the quality of graphene oxide powder. The BET specific surface area represents the graphene oxide powder. Represents the minimum coverage area of ​​a single silane molecule. Represents Avogadro's constant. This represents the molar mass of the silane coupling agent KH-560. This represents the excess reaction coefficient.

[0043] The average diameter of the prepared silane-based graphene conductive filler sheets is 5-10 micrometers, and the average thickness is 1-3 nanometers. BET has a specific surface area of ​​250-350 square meters per gram and a surface grafting rate of 3.5%-5.0%.

[0044] 1000g of graphene oxide powder was weighed and added to a high-pressure reactor containing 50L of ethanol-water solution (ethanol:water volume ratio 9:1). The stirring motor on top of the reactor was turned on and set to 800 rpm. An online homogenizer and an 800W ultrasonic generator were started to exfoliate the mixture for 30 minutes. The BET specific surface area of ​​the graphene oxide powder was determined using a fully automated specific surface area analyzer. The minimum coverage area for a single silane molecule is set at 350 square meters per gram. for The molar mass of silane coupling agent KH-560 per square meter The value is 236.34 grams per mole. The excess reaction coefficient is set. The constant of Avogadro is 5.0. for per mole. Substitute the above parameters into the formula. In the calculation, the required mass of silane coupling agent KH-560 was determined. 1675.7 g of silane coupling agent KH-560 was weighed and dissolved in 3 liters of ethanol-water solution. Hydrolysis was carried out for 20 minutes with stirring at 200 rpm. The hydrolyzed silane solution was pumped into a reactor, and the pH of the system was adjusted to 5.0 using a 1 mol / L sodium hydroxide solution. The oil bath heating system of the reactor was started, and the reaction temperature was raised to 70℃ and maintained at a constant temperature. The grafting reaction was carried out for 6 hours under mechanical stirring and reflux condensation. After the reaction, solid-liquid separation was performed using a tubular centrifuge at 12000 rpm. The solid product was washed with ethanol and dried in a vacuum oven at 60℃ and -0.1 MPa for 12 hours to obtain the silane-based graphene conductive filler. Characterization showed that the average sheet diameter of the silane-based graphene conductive filler was 10 micrometers, the average thickness was 3 nanometers, the BET specific surface area was 350 square meters per gram, and the surface grafting rate was 5.0%.

[0045] S2: Nanoscale tourmaline powder is mixed with cerium nitrate solution for ion adsorption, and then placed in a tube furnace for high-temperature calcination at 600℃ under an inert atmosphere to drive cerium ions to occupy the defect sites in the tourmaline crystal lattice. Rare earth-doped tourmaline composite powder is then prepared by air jet milling.

[0046] The specific steps of ion adsorption in rare earth-doped tourmaline composite powder include: Prepare a cerium nitrate solution with a molar concentration of 0.1-0.2 mol / L; A suspension system was constructed by adding nano-sized tourmaline powder to a cerium nitrate solution; Adjust the pH of the suspension system to 3.5-4.5; The suspension system was subjected to ultrasonic oscillation treatment at a temperature of 40-50℃ for 1-2 hours to allow cerium ions to be adsorbed into the surface pores of nano-scale tourmaline powder. The suspension system was filtered and dried to obtain the doped precursor powder.

[0047] The high-temperature calcination process specifically includes: The doped precursor powder is placed in an alumina crucible and pushed into the isothermal zone of a tube furnace. High-purity nitrogen gas is introduced into the tubular atmosphere furnace, and the gas flow rate is controlled at 200-300 ml per minute; The furnace temperature is raised to 600℃ at a heating rate of 5-8℃ per minute and held for calcination for 2-3 hours, so that the adsorbed cerium ions diffuse into the tourmaline crystal structure. After the furnace has cooled naturally to room temperature, the calcined product is removed. The calcined products were deagglomerated and dispersed using an air jet mill, with the milling pressure controlled at 0.6-0.8 MPa, to obtain rare earth-doped tourmaline composite powder. The median particle size D50 of the prepared rare earth-doped tourmaline composite powder was 0.8-1.5 μm. The normal total emissivity in the 8-14 micrometer band is 0.92-0.96; The mass fraction of rare earth cerium ions is 2.5%-4.0%.

[0048] Prepare 20 liters of cerium nitrate solution with a molar concentration of 0.2 mol / L and add it to a reaction vessel equipped with an ultrasonic vibrating plate. Weigh 5 kg of nano-sized tourmaline powder and add it to the solution, then mechanically stir for 30 minutes. Adjust the pH of the suspension to 4.5 using an ammonia buffer solution. Turn on the heating device to raise the system temperature to 50°C and start the ultrasonic generator for 2 hours. After pressure filtration, washing, and drying, obtain the doped precursor. Load the precursor powder into a corundum crucible and push it into a high-temperature tube furnace. Introduce high-purity nitrogen gas at a flow rate of 300 mL / min. Set the heating program to raise the temperature to 600°C at a rate of 8°C / min and hold for calcination for 3 hours. After natural cooling, send the sintered block into an air jet mill. Set the milling pressure to 0.8 MPa and the classifier speed to 4000 rpm. The test results showed that the median particle size D50 of the rare earth-doped tourmaline composite powder was 1.5 micrometers, the normal total emissivity in the 8-14 micrometer band was 0.96, and the doping mass fraction of rare earth cerium ions was 4.0%.

[0049] S3: The modified waterborne polyurethane resin matrix is ​​pumped into a high-shear emulsifier, and silane-based graphene conductive filler, rare earth-doped tourmaline composite powder and interface compatibilizer are added in sequence. The mixture is then dispersed and mixed at a shear rate of 3000 rpm for 30 minutes to ensure that the filler is evenly distributed in the matrix and to construct a heating slurry.

[0050] The material ratio for preparing the AI ​​intelligent digital graphene heating wall panel is as follows: The modified waterborne polyurethane resin matrix content is 45-60 parts by weight; The content of silane-based graphene conductive filler is 8-15 parts by weight; The rare earth-doped tourmaline composite powder contains 20-30 parts by weight. The interface compatibilizer content is 2-5 parts by weight. The specific steps for constructing the exothermic slurry include: Start the circulating cooling water system of the high-shear emulsifier and control the material temperature between 25-35℃; Add the modified waterborne polyurethane resin matrix into the dispersion vessel and start low-speed stirring. The silane-based graphene conductive filler was added in three batches, and after each addition, it was pre-dispersed at 1000 rpm for 5-10 minutes. Rare earth-doped tourmaline composite powder and interfacial compatibilizer were added, and the rotation speed was increased to 3000 rpm for high-intensity shear dispersion; During the dispersion process, the dispersion vessel is evacuated to -0.08MPa to -0.09MPa to remove air bubbles from the slurry.

[0051] The temperature control system of the high-shear emulsifier is set to maintain the material temperature at 35℃. 60 kg of modified waterborne polyurethane resin matrix is ​​pumped into the dispersion vessel and stirring is started. 15 kg of silane-based graphene conductive filler is weighed and added in three portions. After each addition of 5 kg, dispersion is performed at 1000 rpm for 10 minutes. 30 kg of rare earth-doped tourmaline composite powder and 5 kg of interface compatibilizer are added. The emulsifier speed is increased to 3000 rpm, and shear dispersion is performed for 30 minutes. A two-stage rotary vane vacuum pump is turned on to evacuate the vessel to a vacuum level of -0.09 MPa. After dispersion, the vacuum pump is turned off, and the vacuum is broken back to atmospheric pressure to obtain the exothermic slurry.

[0052] S4: Inject the heating slurry into a metal mold preheated to 120°C, and hold it under pressure of 15MPa for 45 minutes to induce the graphene sheets to align along the plane. After demolding and natural cooling, the AI ​​intelligent digital graphene heating wall panel is prepared.

[0053] The curing process specifically includes: Apply release agent evenly to the inner surface of the metal mold and preheat to 120°C; The degassed heating slurry is quantitatively injected into the cavity of the metal mold; Close the mold and increase the molding pressure to 15MPa at a pressurization rate of 1-2MPa per minute; Maintain a temperature of 120℃ and a pressure of 15MPa for 45 minutes to carry out the cross-linking and curing reaction, so that the resin matrix forms a three-dimensional network structure; Open the mold cooling channel and introduce cooling oil to reduce the mold temperature to below 60°C.

[0054] The method also includes a post-processing step, which includes: Open the metal mold and remove the solidified sheet material; Place the board in a constant temperature forced-air drying oven and perform secondary heat curing at 80℃ for 4-6 hours; The normal total emissivity of the substrate was detected using an infrared spectrometer; The surface sheet resistance of the board is tested using a four-probe tester, and qualified products with a surface sheet resistance in the range of 10-50 ohms are screened.

[0055] Preheat the mold to 120°C and spray with a high-temperature release agent. Pour the slurry prepared in step S3 into the mold. After closing the mold, execute the pressurization program, setting the pressurization rate to 2 MPa per minute, and increase the pressure to 15 MPa. Maintain 120°C and 15 MPa pressure for curing for 45 minutes. Introduce cooling medium to reduce the mold temperature to below 60°C, then open the mold and remove the sheet material.

[0056] The board was placed in a forced-air drying oven and subjected to secondary heat curing at 80℃ for 6 hours. The normal total emissivity was measured using an infrared emissivity meter, and the surface sheet resistance was measured at test points selected at the diagonal and center positions of the board using a four-probe tester.

[0057] Table 3. Experimental Test Results of Example 2 ; Table 3 presents the specific test data for the AI ​​intelligent digital graphene heating wall panel prepared in Example 2.

[0058] Table 4 Comparison of Product Performance in Example 2 ; Table 4 shows a comparison of the key performance indicators of the product of Example 2 and the existing conventional carbon crystal heating plate.

[0059] The above embodiments illustrate preferred embodiments of the present invention. Any equivalent adjustments to the technical solution based on chemical engineering methods are within the scope of protection, including but not limited to: using different chemical reaction processes to achieve technical effects, optimizing the production process flow, adjusting the raw material ratio scheme, improving reactor design, and improving energy efficiency. Any implementation scheme derived from reasonable modifications to the production process, raw material utilization, equipment configuration, or system integration level without departing from the core technology of the present invention should be considered within the protection scope defined by the technical solution of the present invention.

Claims

1. An AI-powered intelligent digital graphene heating wall panel, characterized in that, The materials used to prepare the AI ​​intelligent digital graphene heating wall panel include: (a) Modified waterborne polyurethane resin matrix, the content of which is 45-60 parts by weight; (b) Silane-based graphene conductive filler, the content of which is 8-15 parts by weight; (c) Rare earth doped tourmaline composite powder, the content of which is 20-30 parts by weight; (d) Interface compatibilizer, the content of which is 2-5 parts by weight.

2. The AI ​​intelligent digital graphene heating wall panel according to claim 1, characterized in that, The average diameter of the silane-based graphene conductive filler sheets is 5-10 micrometers. The average thickness of the silane-based graphene conductive filler is 1-3 nanometers. The BET specific surface area of ​​the silane-based graphene conductive filler is 250-350 square meters per gram. The surface grafting rate of the silane-based graphene conductive filler is 3.5%-5.0%.

3. The AI ​​intelligent digital graphene heating wall panel according to claim 1, characterized in that, The median particle size D50 of the rare earth-doped tourmaline composite powder is 0.8-1.5 micrometers; The rare earth-doped tourmaline composite powder has a normal total emissivity of 0.92-0.96 in the 8-14 micrometer wavelength band; The rare earth doped tourmaline composite powder has a doping mass fraction of 2.5%-4.0% for cerium ions.

4. The AI ​​intelligent digital graphene heating wall panel according to claim 1, characterized in that, The preparation method of the AI ​​intelligent digital graphene heating wall panel includes the following steps: S1: Graphene oxide powder is dispersed in an ethanol aqueous solution, mixed with silane coupling agent KH-560 and the pH value is adjusted to 4.0-5.

0. Grafting reaction is carried out under ultrasonic power of 800W to condense the silanol groups generated by silane hydrolysis with the hydroxyl groups on the graphene surface. The silane-based graphene conductive filler is prepared by centrifugation and vacuum drying. S2: Nanoscale tourmaline powder is mixed with cerium nitrate solution for ion adsorption, and then placed in a tube furnace for high-temperature calcination at 600°C under an inert atmosphere to drive cerium ions to occupy the defect sites in the tourmaline crystal lattice. The rare earth-doped tourmaline composite powder is then prepared by air jet milling. S3: The modified waterborne polyurethane resin matrix is ​​pumped into a high-shear emulsifier, and the silane-based graphene conductive filler, the rare earth-doped tourmaline composite powder and the interface compatibilizer are added in sequence. The mixture is then dispersed and mixed at a shear rate of 3000 rpm for 30 minutes to ensure that the filler is evenly distributed in the matrix and to construct a heating slurry. S4: The heating slurry is injected into a metal mold preheated to 120°C and cured under pressure of 15MPa for 45 minutes to induce the graphene sheets to align along the plane. The AI ​​intelligent digital graphene heating wall panel is then prepared by demolding and natural cooling.

5. The AI ​​intelligent digital graphene heating wall panel according to claim 4, characterized in that, The preparation process of the silane-based graphene conductive filler specifically includes: The BET specific surface area of ​​the graphene oxide powder was determined. The theoretical grafting amount of the silane coupling agent KH-560 is calculated using the following formula: ； Dissolve the calculated amount of the silane coupling agent KH-560 in a mixed solvent of ethanol and water and stir to hydrolyze for 15-20 minutes; The graphene oxide powder was added to the hydrolyzed silane solution and grafted in a constant temperature water bath at 60-70°C for 4-6 hours. in, This represents the mass of the silane coupling agent KH-560. This represents the mass of the graphene oxide powder. The BET specific surface area represents the graphene oxide powder. Represents the minimum coverage area of ​​a single silane molecule. Represents Avogadro's constant. This represents the molar mass of the silane coupling agent KH-560. This represents the excess reaction coefficient.

6. The AI ​​intelligent digital graphene heating wall panel according to claim 4, characterized in that, The ion adsorption step in the rare earth-doped tourmaline composite powder specifically includes: Prepare a cerium nitrate solution with a molar concentration of 0.1-0.2 mol / L; The nano-sized tourmaline powder was added to the cerium nitrate solution to construct a suspension system; Adjust the pH of the suspension system to 3.5-4.5; The suspension system was subjected to ultrasonic oscillation treatment at a temperature of 40-50℃ for 1-2 hours to allow cerium ions to be adsorbed into the surface pores of the nano-scale tourmaline powder. The suspension system was filtered and dried to obtain the doped precursor powder.

7. The AI ​​intelligent digital graphene heating wall panel according to claim 4, characterized in that, The high-temperature calcination step in the rare earth-doped tourmaline composite powder specifically includes: The doped precursor powder is placed in an alumina crucible and pushed into the isothermal zone of a tube furnace. High-purity nitrogen gas is introduced into the tubular atmosphere furnace, and the gas flow rate is controlled at 200-300 ml per minute; The furnace temperature is raised to 600℃ at a heating rate of 5-8℃ per minute and held for calcination for 2-3 hours, so that the adsorbed cerium ions diffuse into the tourmaline crystal structure. After the furnace has cooled naturally to room temperature, the calcined product is removed. The calcined product was deagglomerated and dispersed using an air jet mill, with the milling pressure controlled at 0.6-0.8 MPa, to obtain the rare earth-doped tourmaline composite powder.

8. The AI ​​intelligent digital graphene heating wall panel according to claim 4, characterized in that, The specific steps for constructing the heating slurry include: Start the circulating cooling water system of the high-shear emulsifier to control the material temperature between 25-35℃; The modified waterborne polyurethane resin matrix is ​​added into a dispersion vessel and low-speed stirring is started. The silane-based graphene conductive filler was added in three batches, and after each addition, it was pre-dispersed at 1000 rpm for 5-10 minutes. The rare earth-doped tourmaline composite powder and the interface compatibilizer were added, and the rotation speed was increased to 3000 rpm for high-intensity shear dispersion. During the dispersion process, the dispersion vessel is evacuated to -0.08MPa to -0.09MPa to remove air bubbles from the slurry.

9. The AI ​​intelligent digital graphene heating wall panel according to claim 4, characterized in that, The curing steps of the AI ​​intelligent digital graphene heating wall panel specifically include: A release agent is uniformly sprayed onto the inner surface of the metal mold and preheated to 120°C; The degassed heating slurry is quantitatively injected into the cavity of the metal mold; Close the mold and increase the molding pressure to 15MPa at a pressurization rate of 1-2MPa per minute; Maintain a temperature of 120℃ and a pressure of 15MPa for 45 minutes to carry out the cross-linking and curing reaction, so that the resin matrix forms a three-dimensional network structure; Open the mold cooling channel and introduce cooling oil to reduce the mold temperature to below 60°C.

10. The AI ​​intelligent digital graphene heating wall panel according to claim 4, characterized in that, The preparation method of the AI ​​intelligent digital graphene heating wall panel further includes a post-processing step, which includes: Open the metal mold and remove the solidified sheet material; Place the board in a constant temperature forced-air drying oven and perform secondary heat curing at 80℃ for 4-6 hours; The normal total emissivity of the substrate was detected using an infrared spectrometer; The surface sheet resistance of the board is tested using a four-probe tester, and qualified products with a surface sheet resistance in the range of 10-50 ohms are screened.

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