A DC low-power nanoscale semiconductor electric heat tracing diaphragm

Abstract

The present invention discloses a DC low-power nanoscale semiconductor electric heat tracing diaphragm. The present invention relates to the technical field of electric heat tracing diaphragms, and includes preparing a heating layer and preparing an electrode layer. An insulating buffer layer is added between the heating layer and the electrode layer to form the electric heat tracing diaphragm. The advantages of the present invention are as follows: By uniformly dispersing nanoparticles in the organic semiconductor, the local resistance of the heating layer can be effectively adjusted. Since the size of the nanoparticles is small and the distribution is uniform, the phenomenon of hot spots or cold spots caused by too large or too small local resistance can be avoided. The interaction between the nanoparticles and the organic semiconductor can inhibit heat accumulation. During the heating process, the organic semiconductor may experience a decrease in material performance or local thermal stress due to excessive local heat. When local heat concentration occurs, the nanoparticles can absorb the excess heat and evenly disperse the heat to the surrounding organic semiconductor materials through heat conduction, thus avoiding the phenomenon of local overheating.

Description

Technical Field

[0001] The present invention relates to the technical field of electric tracing diaphragms, and specifically to a DC low-power nanoscale semiconductor electric tracing diaphragm. Background Art

[0002] In industries such as petroleum, chemical engineering, and natural gas, a large number of pipelines are used to transport various fluids. When in a cold environment or transporting fluids that are prone to solidification or have high viscosity (such as crude oil and heavy oil), it is necessary to trace heat the pipelines. The electric tracing diaphragm can be closely attached to the surface of the pipeline, effectively maintaining the pipeline temperature and ensuring the smooth transportation of the fluid. In buildings, it can be used for floor heating, roof snow melting and ice removal, etc. In the floor heating system, the electric tracing diaphragm is installed under the floor, and the floor temperature can be precisely controlled by adjusting the current magnitude, providing a comfortable heating environment indoors. In terms of roof snow melting and ice removal, the electric tracing diaphragm can prevent snow from accumulating and freezing on the roof, avoiding damage to the building structure caused by the accumulation of ice and snow, and at the same time reducing the threat to pedestrian safety caused by the falling of ice and snow;

[0003] It is difficult to achieve completely uniform distribution of the heating material in the traditional electric heating wire heating electric tracing diaphragm, which causes local overheating or overcooling of the electric tracing diaphragm during operation. If the spacing design of the electric heating wires is unreasonable or the electric heating wires are displaced during the installation process, it will lead to uneven heating. Therefore, we propose a DC low-power nanoscale semiconductor electric tracing diaphragm. Summary of the Invention

[0004] The purpose of the present invention is to provide a DC low-power nanoscale semiconductor electric tracing diaphragm.

[0005] To solve the problems raised in the above background art, the present invention provides the following technical solution: A DC low-power nanoscale semiconductor electric tracing diaphragm, including preparing a heating layer, preparing an electrode layer, and adding a heat insulation buffer layer between the heating layer and the electrode layer to make the electric tracing diaphragm. The specific preparation steps of the DC low-power nanoscale semiconductor electric tracing diaphragm are as follows:

[0006] Step 1: Compound an organic semiconductor material with nano silver particles to make a nano-organic semiconductor ink, and spray the nano-organic semiconductor ink on the surface of the substrate through an inkjet printer to make a heating layer;

[0007] Step 2: Etch micro-nano grooves on the surface of the heating layer substrate through a mold with a groove pattern;

[0008] Step 3: Use three materials, titanium, manganese dioxide, and gold, for sequential deposition to prepare a layered composite electrode layer, and perform interface treatment between the interfaces of each electronic grade layer to enhance the bonding force and charge transfer performance between each electronic electrode layer;

[0009] Step 4: Prepare composite fibers with a hollow structure using nano-organic semiconductor materials;

[0010] Step 5: Use the interweaving method to interweave two fiber bundles with different properties to make a heat-insulating buffer layer;

[0011] Step 6: Assemble the heating layer, the electrode layer and the heat-insulating buffer layer into an electric tracing diaphragm, conduct performance tests and quality inspections, and package the qualified electric tracing diaphragms;

[0012] In the said Step 2, use an electron beam lithography machine to draw a wavy micro-nano groove pattern on the surface of the silicon mold. The wavelength of the wave is set to 1 μm - 10 μm, the amplitude is 100 nm - 500 nm, the width of the groove is set to 50 nm - 500 nm, the depth is set to 100 nm - 1000 nm, the spacing between adjacent grooves is set to 200 nm - 1000 nm, the acceleration voltage of the electron beam lithography machine is set to 5 kV - 30 kV, the beam current is set to 1 nA - 10 nA. Place the silicon mold with the micro-nano groove pattern on the surface of the heating layer material, and put it into a hot embossing device. Press at a temperature of 100°C - 150°C under a pressure of 50 MPa - 100 MPa for 5 min - 10 min. After the pressing is completed, use oxygen plasma to transfer the groove pattern to the heating layer material. The etching power is set to 50 W - 200 W, the air pressure is set to 0.5 Pa - 5 Pa, and the etching time is 10 min - 60 min. Etch a wavy micro-nano groove pattern on the surface of the heating layer;

[0013] In the said Step 3, use titanium as the bottom layer in the composite electrode layer, and deposit a titanium layer with a thickness of 10 nm - 100 nm on the substrate by magnetron sputtering technology. Use chemical adsorption to introduce hydroxyl groups on the surface of the titanium layer. Immerse the substrate with the titanium layer in a solution containing hydrogen peroxide and sodium hydroxide, and react at a temperature of 40°C - 60°C for 30 min - 60 min to form a hydroxylated surface layer on the surface of the titanium layer. Then transfer the substrate to a solution containing manganese ions, and make the manganese ions adsorb on the hydroxylated titanium layer surface through Ti - O - Mn chemical bonds. Use manganese dioxide as the intermediate layer in the composite electrode layer, and deposit a manganese dioxide layer with a thickness of 100 nm - 500 nm on the surface of the bottom layer by chemical deposition method. Place the substrate in a plasma processing device, introduce oxygen as the reaction gas, adjust the radio frequency power between 50 W - 200 W, and the processing time is 5 min - 30 min. Oxygen plasma generates oxygen free radicals and peroxy free radicals on the surface of manganese dioxide. Use gold as the top layer in the composite electrode layer, and deposit a gold layer with a thickness of 50 nm - 200 nm on the intermediate layer by magnetron sputtering technology to prepare the electrode layer in the electric tracing diaphragm.

[0014] As a further solution of the present invention: in the step one, silver nanoparticles are dispersed in a sodium dodecyl sulfate solution to prepare a silver nanoparticle dispersion. The concentration of sodium dodecyl sulfate is set to 1%-5% of the mass of silver nanoparticles. Prepare 3-hexylthiophene monomers with a purity of 99%. Under nitrogen protection, dissolve the 3-hexylthiophene monomers in anhydrous chloroform to make a solution with a concentration of 0.1mol / L - 0.5mol / L. Then add ferric chloride initiator to the solution. The molar ratio of ferric chloride to 3-hexylthiophene monomers is set to 0.01 - 0.1. Stir at a rate of 60r / min - 100r / min for 24h - 48h at a temperature of 0℃ - 5℃ to obtain a mixed solution. Then add the silver nanoparticle dispersion to the mixed solution and disperse it for 30min - 60min at a frequency of 30kHz - 50kHz using an ultrasonic disperser to obtain a nano-organic semiconductor ink.

[0015] As a further solution of the present invention: in the step one, use polyimide polymer as the base material of the electric heat tracing diaphragm. Load the nano-organic semiconductor ink into the ink cartridge of an inkjet printer. Use the nozzle to spray the nano-organic semiconductor ink on the surface of the base to form a pattern. The spraying frequency of the nozzle is set to 1kHz - 10kHz, and the distance between the nozzle and the base is set to 0.1mm - 1mm. Spray a nano-organic semiconductor ink with a thickness of 100um - 500um on the surface of the base. Add the base sprayed with nano-organic semiconductor ink to a drying oven for drying. The drying temperature is set to 60℃ - 100℃, and the drying time is set to 10min - 30min to make the heating layer in the electric heat tracing diaphragm.

[0016] As a further solution of the present invention: in the step four, dissolve 4,4 、 -diaminodiphenyl ether in an N-methyl-2-pyrrolidone solution to prepare a diamine solution, 4,4 、- The concentration of diaminodiphenyl ether is set to 0.1 mol / L - 0.5 mol / L. Then, pyromellitic dianhydride is added to the diamine solution, and the molar ratio of diamine to dianhydride is set to 1:1. The mixed solution is added to an electric stirrer and stirred at a rate of 60 r / min - 100 r / min for 4 h - 8 h at a temperature of 0°C - 5°C to obtain a polyamic acid solution. Boron nitride particles with a particle size of 10 nm - 100 nm are selected. The boron nitride particles are added to an N-methyl-2-pyrrolidone solution, and then a polyvinylpyrrolidone dispersant is added. The dosage of polyvinylpyrrolidone is 1% - 5% of the mass of the boron nitride nanoparticles. The mixed solution is added to an ultrasonic disperser and dispersed at a frequency of 20 kHz - 40 kHz for 30 min - 60 min to obtain a boron nitride nanoparticle dispersion. The boron nitride nanoparticle dispersion is added to the polyamic acid solution to prepare an outer tube solution. The addition amount of boron nitride nanoparticles accounts for 1% - 10% of the mass of the polyamic acid. Polyvinyl alcohol is dissolved in water to prepare an inner tube solution with a concentration of 5% - 10%.

[0017] As a further scheme of the present invention: in the fourth step, the inner tube solution is added to the inner tube of a coaxial electrospinning device, and the outer tube solution is added to the outer tube of the coaxial electrospinning device. The flow rate of the inner tube solution is set to 0.1 mL / h - 0.5 mL / h, the flow rate of the outer tube solution is set to 0.5 mL / h - 2 mL / h, the electrospinning voltage is set to 10 kV - 30 kV, and the distance between the spinneret and the receiving device is set to 10 cm - 30 cm. The spinning equipment is started to simultaneously eject the inner tube solution and the outer tube solution from the concentric spinneret to form composite fibers with a diameter of 10 μm - 100 μm. The composite fibers aggregate on the receiving device to form a fiber mat. The collected fiber mat is placed in an oven for thermal imidization treatment. First, it is maintained at a temperature of 100°C - 150°C for 1 h - 2 h, and then the temperature is raised to 200°C - 300°C at a rate of 2°C / min - 5°C / min and maintained for 2 h - 4 h to imidize the polyamic acid and simultaneously cure the fiber structure. Then, the cured fibers are soaked in water and soaked at a temperature of 40°C - 60°C for 1 h - 2 h to dissolve the polyvinyl alcohol and exude it from the fibers, leaving a hollow pipe structure to prepare polyimide fibers with a hollow structure.

[0018] As a further scheme of the present invention: in the fifth step, the polyimide fibers are made into fiber bundles with a linear density of 10 tex - 100 tex, and the T700 type carbon fibers are made into fiber bundles with a linear density of 5 tex - 80 tex. The mass ratio of polyimide fibers to carbon fibers is 3:1. The prepared polyimide fiber bundles and carbon fiber bundles are respectively placed in two feeding devices of an air interlacing machine. The air pressure of the air interlacing machine is set to 0.1 MPa - 0.5 MPa, and the air flow rate is set to 10 m 3 / h - 50 m 3 / h, the angle of the nozzle is set at 30° - 60°, the feeding speed is set at 10 m / min - 50 m / min. Under the action of the air flow pressure and flow rate, the two fiber bundles are blown apart and mixed with each other in the interweaving area. After the fiber fabric is interwoven, it is put into a heat setting device and processed at a temperature of 180°C - 250°C for 1 min - 5 min to be shaped into the heat insulation buffer layer in the electric heat tracing diaphragm.

[0019] As a further solution of the present invention: In step six, the heating layer and the electrode layer are put into an ultrasonic cleaning machine, and ethanol is selected as the ultrasonic cleaning liquid to remove the dust and trace impurities on the surfaces of the heating layer and the electrode layer. The loose fibers and dust on the surface of the heat insulation buffer layer fiber fabric are removed by compressed air. Wires are welded to the lead-out ends of the electrode layer. After welding, the welding parts are encapsulated and protected with insulating glue. Epoxy resin is coated along the edge of the electric heat tracing diaphragm to form a closed border with a width of 2 mm - 10 mm, fixing the heating layer, the electrode layer and the heat insulation buffer layer together. Check the dislocation, wrinkles and protrusions between the layers of the assembled electric heat tracing diaphragm. Use an insulation resistance tester to detect the resistance value between the electrode layers, the insulation resistance between the electrode layer and the heating layer, and the insulation resistance between the electrode layer and the external package. After cleaning the surface of the qualified electric heat tracing diaphragm, place it on an anti-static polyethylene foam. Put the electric heat tracing diaphragm wrapped with protective materials into an aluminum foil composite film, and use a heat sealer to heat seal the edge of the aluminum foil composite film. The heat sealing temperature is set at 120°C - 180°C, and the heat sealing width is set at 5 mm - 10 mm.

[0020] Adopting the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] 1. By uniformly dispersing the nanoparticles in the organic semiconductor, the present invention can effectively adjust the local resistance of the heating layer. Since the nanoparticles are small in size and evenly distributed, it can avoid the hot spot or cold spot phenomenon caused by too large or too small local resistance. The interaction between the nanoparticles and the organic semiconductor can inhibit heat aggregation. During the heating process of the organic semiconductor, the material performance may decline or local thermal stress may be generated due to excessive local heat. When local heat concentration occurs, the nanoparticles can absorb the excess heat and evenly disperse the heat to the surrounding organic semiconductor materials through heat conduction, thus avoiding the local overheating phenomenon and ensuring the uniformity of heating;

[0022] 2. Through the interweaving method, the hollow polyimide fibers and carbon fibers in the present invention are interwoven with each other to form a complex fiber network structure, which can effectively prevent the direct transfer of heat, making the heat conduction path between the fibers tortuous. The high thermal conductivity of the carbon fibers can also be utilized in this structure. It can quickly disperse local heat, avoid heat concentration at a certain point, and at the same time, restricted by the heat insulation effect of the hollow polyimide fibers, it cannot conduct heat outward quickly, thereby further improving the overall heat insulation performance of the heat insulation buffer layer. The interwoven structure enables a synergistic effect between the hollow polyimide fibers and the carbon fibers. The two fibers are wound and interwoven with each other, making their combination tighter and capable of effectively transmitting stress. This synergistic effect not only improves the tensile strength of the buffer layer but also enhances its bending strength and fatigue resistance.

[0023] 3. By etching micro-nano grooves on the surface of the heating layer in the present invention, the contact surface area between the heating layer and the adjacent medium can be significantly increased. The micro-nano grooves guide heat to conduct along a specific path. When the heating layer generates heat, the heat will preferentially propagate along the direction of the grooves. This directional heat conduction method can reduce the disordered diffusion of heat inside the heating layer, making the heat transfer to the area that needs to be heated faster and more concentrated. The micro-nano grooves disperse the heat generated by the heating layer more evenly. Due to the existence of the grooves, heat will not accumulate locally on the surface of the heating layer but is redistributed over the entire surface of the heating layer through the grooves. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of the preparation process of the DC low-power nano-scale semiconductor electric heating film in the embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] The following further describes the specific embodiments of the present invention with reference to the drawings. It should be noted here that the description of these embodiments is for helping to understand the present invention, but does not constitute a limitation to the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0026] A DC low-power nano-scale semiconductor electric heating film of the present invention includes preparing a heating layer, preparing an electrode layer, and adding a heat insulation buffer layer between the heating layer and the electrode layer to make the electric heating film. The specific preparation steps of the DC low-power nano-scale semiconductor electric heating film are as follows:

[0027] Step 1: Compound an organic semiconductor material with nano-silver particles to make a nano-organic semiconductor ink, and spray the nano-organic semiconductor ink on the surface of the substrate through an inkjet printer to make a heating layer;

[0028] Step 2: Etch micro-nano grooves on the surface of the heating layer substrate through a mold with a groove pattern;

[0029] Step 3: Sequentially deposit three materials, titanium, manganese dioxide, and gold, to prepare a layered composite electrode layer, and perform interface treatment between each electronic-grade layer to enhance the bonding force and charge transfer performance between each electronic electrode layer;

[0030] Step 4: Use nano-organic semiconductor materials to prepare composite fibers with a hollow structure;

[0031] Step 5: Use the interweaving method to interweave two fiber bundles with different properties to form a heat-insulating buffer layer;

[0032] Step 6: Assemble the heating layer, the electrode layer, and the heat-insulating buffer layer into an electric tracing diaphragm, and perform performance testing and quality inspection. Package the qualified electric tracing diaphragms;

[0033] In Step 2, use an electron beam lithography machine to draw a wavy micro-nano groove pattern on the surface of a silicon mold. The wavelength of the wave is set to 1 μm - 10 μm, the amplitude is 100 nm - 500 nm, the width of the groove is set to 50 nm - 500 nm, the depth is set to 100 nm - 1000 nm, the spacing between adjacent grooves is set to 200 nm - 1000 nm, the acceleration voltage of the electron beam lithography machine is set to 5 kV - 30 kV, and the beam current is set to 1 nA - 10 nA. Place the silicon mold with the micro-nano groove pattern on the surface of the heating layer material, and put it into a hot embossing device. Press at a temperature of 100°C - 150°C and a pressure of 50 MPa - 100 MPa for 5 min - 10 min. After the pressing is completed, use oxygen plasma to transfer the groove pattern to the heating layer material. The etching power is set to 50 W - 200 W, the air pressure is set to 0.5 Pa - 5 Pa, and the etching time is 10 min - 60 min. Etch a wavy micro-nano groove pattern on the surface of the heating layer;

[0034] In Step 3, titanium is used as the bottom layer in the composite electrode layer. A titanium layer with a thickness of 10 nm - 100 nm is deposited on the substrate by magnetron sputtering technology. Hydroxyl groups are introduced on the surface of the titanium layer by chemical adsorption. The substrate with the titanium layer is immersed in a solution containing hydrogen peroxide and sodium hydroxide and reacted at a temperature of 40°C - 60°C for 30 min - 60 min to form a hydroxylated surface layer on the titanium layer. Then the substrate is transferred to a solution containing manganese ions, and the manganese ions are adsorbed on the surface of the hydroxylated titanium layer through Ti - O - Mn chemical bonds. Manganese dioxide is used as the intermediate layer in the composite electrode layer, and a manganese dioxide layer with a thickness of 100 nm - 500 nm is deposited on the surface of the bottom layer by chemical deposition method. The substrate is placed in a plasma processing device, oxygen is introduced as the reaction gas, the radio frequency power is adjusted between 50 W - 200 W, and the processing time is 5 min - 30 min. Oxygen plasma generates oxygen free radicals and peroxy free radicals on the surface of manganese dioxide. Gold is used as the top layer in the composite electrode layer, and a gold layer with a thickness of 50 nm - 200 nm is deposited on the intermediate layer by magnetron sputtering technology to prepare the electrode layer in the electric heat tracing membrane.

[0035] In an embodiment of the present invention: In Step 1, nano - silver particles are dispersed in a sodium dodecyl sulfate solution to prepare a nano - silver particle dispersion solution. The concentration of sodium dodecyl sulfate is set to 1% - 5% of the mass of the nano - silver particles. 3 - hexylthiophene monomers with a purity of 99% are prepared. Under nitrogen protection, the 3 - hexylthiophene monomers are dissolved in anhydrous chloroform to form a solution with a concentration of 0.1 mol / L - 0.5 mol / L. Then an iron(III) chloride initiator is added to the solution, and the molar ratio of iron(III) chloride to 3 - hexylthiophene monomers is set to 0.01 - 0.1. The mixture is stirred at a rate of 60 r / min - 100 r / min at a temperature of 0°C - 5°C for 24 h - 48 h to obtain a mixed solution. Then the nano - silver particle dispersion solution is added to the mixed solution, and the mixture is dispersed by an ultrasonic disperser at a frequency of 30 kHz - 50 kHz for 30 min - 60 min to obtain a nano - organic semiconductor ink.

[0036] In an embodiment of the present invention: In Step 1, a polyimide polymer is used as the substrate material of the electric heat tracing membrane. The nano - organic semiconductor ink is loaded into the ink cartridge of an inkjet printer, and the nano - organic semiconductor ink is sprayed on the surface of the substrate by a nozzle to form a pattern. The spraying frequency of the nozzle is set to 1 kHz - 10 kHz, the distance between the nozzle and the substrate is set to 0.1 mm - 1 mm, and a nano - organic semiconductor ink layer with a thickness of 100 μm - 500 μm is sprayed on the surface of the substrate. The substrate sprayed with the nano - organic semiconductor ink is placed in an oven for drying. The drying temperature is set to 60°C - 100°C, and the drying time is set to 10 min - 30 min to prepare the heating layer in the electric heat tracing membrane.

[0037] In one embodiment of the present invention: In step four, 4,4 、 -diaminodiphenyl ether is dissolved in N-methyl-2-pyrrolidone solution to prepare a diamine solution, and the concentration of 4,4 、 -diaminodiphenyl ether is set to 0.1 mol / L - 0.5 mol / L. Then, pyromellitic dianhydride is added to the diamine solution, and the molar ratio of diamine to dianhydride is set to 1:1. The mixed solution is added to an electric stirrer and stirred at a rate of 60 r / min - 100 r / min for 4 h - 8 h at a temperature of 0°C - 5°C to obtain a polyamic acid solution. Boron nitride particles with a particle size of 10 nm - 100 nm are selected, and the boron nitride particles are added to N-methyl-2-pyrrolidone solution. Then, polyvinylpyrrolidone dispersant is added, and the dosage of polyvinylpyrrolidone is 1% - 5% of the mass of the boron nitride nanoparticles. The mixed solution is added to an ultrasonic disperser and dispersed at a frequency of 20 kHz - 40 kHz for 30 min - 60 min to obtain a boron nitride nanoparticle dispersion. The boron nitride nanoparticle dispersion is added to the polyamic acid solution to prepare an outer tube solution, and the addition amount of the boron nitride nanoparticles accounts for 1% - 10% of the mass of the polyamic acid. Polyvinyl alcohol is dissolved in water to prepare an inner tube solution with a concentration of 5% - 10%.

[0038] In one embodiment of the present invention: In step four, the inner tube solution is added to the inner tube of a coaxial electrospinning device, and the outer tube solution is added to the outer tube of the coaxial electrospinning device. The flow rate of the inner tube solution is set to 0.1 mL / h - 0.5 mL / h, the flow rate of the outer tube solution is set to 0.5 mL / h - 2 mL / h, the electrospinning voltage is set to 10 kV - 30 kV, and the distance between the spinneret and the receiving device is set to 10 cm - 30 cm. The spinning device is started to simultaneously eject the inner tube solution and the outer tube solution from the concentric spinneret to form composite fibers with a diameter of 10 μm - 100 μm. The composite fibers aggregate on the receiving device to form a fiber mat. The collected fiber mat is placed in an oven for thermal imidization treatment. First, it is maintained at a temperature of 100°C - 150°C for 1 h - 2 h, and then heated at a rate of 2°C / min - 5°C / min to 200°C - 300°C and maintained for 2 h - 4 h to imidize the polyamic acid and simultaneously solidify the fiber structure. Then, the cured fiber is soaked in water and soaked at a temperature of 40°C - 60°C for 1 h - 2 h to dissolve the polyvinyl alcohol and exude it from the fiber, leaving a hollow tube structure, thereby preparing polyimide fibers with a hollow structure.

[0039] In an embodiment of the present invention: In step five, the polyimide fibers are made into fiber bundles with a linear density of 10 tex - 100 tex, and the carbon fibers of T700 model are made into fiber bundles with a linear density of 5 tex - 80 tex. The mass ratio of the polyimide fibers to the carbon fibers is 3:1. The prepared polyimide fiber bundles and carbon fiber bundles are respectively placed in two feeding devices of an air interlacing machine. The air pressure of the air interlacing machine is set to 0.1 MPa - 0.5 MPa, and the air flow rate is set to 10 m 3 / h - 50 m 3 / h. The angle of the nozzle is set to 30° - 60°, and the feeding speed is set to 10 m / min - 50 m / min. Under the action of the air pressure and flow rate, the two fiber bundles are blown apart and mixed with each other in the interlacing area. The interlaced fiber fabric is put into a heat setting device and processed at a temperature of 180°C - 250°C for 1 min - 5 min for setting to make the heat insulation buffer layer in the electric heating film.

[0040] In an embodiment of the present invention: In step six, the heating layer and the electrode layer are added to an ultrasonic cleaning machine, and ethanol is selected as the ultrasonic cleaning liquid to remove the dust and trace impurities on the surfaces of the heating layer and the electrode layer. The loose fibers and dust on the surface of the heat insulation buffer layer fiber fabric are removed by compressed air. Wires are welded to the lead-out ends of the electrode layer. After welding, the welding parts are encapsulated and protected with insulating glue. Epoxy resin is coated along the edge of the electric heating film to form a closed border with a width of 2 mm - 10 mm, fixing the heating layer, the electrode layer and the heat insulation buffer layer together. Check the dislocation, wrinkles and protrusions between the layers of the assembled electric heating film. Use an insulation resistance tester to detect the resistance value between the electrode layers, the insulation resistance between the electrode layer and the heating layer, and the insulation resistance between the electrode layer and the external package. After cleaning the surface of the qualified electric heating film, place it on an anti-static polyethylene foam. Put the electric heating film wrapped with protective materials into an aluminum foil composite film, and use a heat sealer to heat-seal the edge of the aluminum foil composite film. The heat-sealing temperature is set to 120°C - 180°C, and the heat-sealing width is set to 5 mm - 10 mm.

[0041] Example 1. Interface treatment is carried out between the titanium layer and the manganese dioxide intermediate layer. Through the Ti - O - Mn chemical bond, manganese ions are adsorbed on the surface of the hydroxylated titanium layer, providing better binding sites for the subsequent deposition of manganese dioxide, thereby improving the interfacial adhesion and charge transfer performance. Interface treatment is carried out between the manganese dioxide intermediate layer and the gold layer, such as oxygen free radicals (·O) and peroxyl radicals (·O2 -), these active species can form stronger chemical bonds with the gold layer during deposition, improving the bonding strength of the interface and the electron transport performance. Through interface treatment, the contact resistance between adjacent layers of materials is reduced, enabling charges to be transmitted more smoothly between the layers. The energy level structure of the transition layer material can better match the energy levels of the adjacent two layers of materials, facilitating electron transition and transport. During the electric tracing process, good charge transport performance can ensure uniform current distribution in the electrode layer, reduce local overheating, and improve the heating efficiency. The interface treatment measures enhance the adhesion between the layers, preventing delamination during use. After chemical adsorption or plasma treatment, the bonding force between adjacent layers is increased, and this enhanced adhesion can ensure the structural integrity of the electrode layer under long-term complex working conditions such as thermal cycling and mechanical vibration, extending the service life of the electric tracing diaphragm.

[0042] Example 2: Fabricate a metal frame that matches the size of the heating layer, place the heating layer inside the frame to fix it in a predetermined position. Apply a layer of conductive adhesive with a thickness of 50 μm evenly on the bonding surface of the electrode layer, then accurately place the electrode layer in the corresponding position of the heating layer, and gently roll it with a rubber roller to remove the air bubbles between the bonding surfaces, ensuring that the electrode layer is closely attached to the heating layer and the conductive adhesive is evenly distributed. Then place the thermal insulation buffer layer between the heating layer and the electrode layer, and use the hot pressing method to bond the thermal insulation buffer layer to the heating layer and the electrode layer at a temperature of 150 °C and a pressure of 2 MPa, so that the fibers are intertwined with each other and tightly combined with the adjacent layers, improving the thermal insulation effect and the overall structural stability. Weld wires at the lead-out end of the electrode layer, and after welding, use insulating glue to encapsulate and protect the welding part. Apply a closed border with a width of 5 mm along the edge of the electric tracing diaphragm using epoxy resin.

[0043] Example 3: Use an electron beam lithography machine to draw a wavy micro-nano groove pattern on the surface of a silicon mold. The wavelength of the wave is set to 5 μm, the amplitude is 300 nm, the width of the groove is set to 200 nm, the depth is set to 5000 nm, and the spacing between adjacent grooves is set to 5000 nm. The acceleration voltage of the electron beam lithography machine is set to 20 kV, and the beam current is set to 50 nA. Place the silicon mold with the micro-nano groove pattern on the surface of the heating layer material and put it into a hot embossing device. Press it at a temperature of 120 °C and a pressure of 80 MPa for 80 min. After the embossing is completed, use oxygen plasma to transfer the groove pattern to the heating layer material. The etching power is set to 100 W, the gas pressure is set to 3 Pa, and the etching time is 40 min. A wavy micro-nano groove pattern is etched on the surface of the heating layer. The micro-nano grooves can enhance the mechanical interlock between the heating layer and the adjacent materials. The presence of the grooves can also increase the chemical interaction between the heating layer and the adjacent materials. Since the grooves increase the contact area, there are more opportunities for chemical reactions or physical adsorption between the heating layer and the adjacent materials.

[0044] As shown in the Figure 1 accompanying drawings, by using a composite material of an organic semiconductor and nanoparticles and making a composite heat-insulating and buffering layer from hollow polyimide fibers and carbon fibers by an interweaving method, the properties of different materials can be combined to produce a synergistic effect, thereby increasing the service life of the electric heating film.

[0045] The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the described embodiments. For those skilled in the art, without departing from the principle and spirit of the present invention, various changes, modifications, substitutions, and variations made to these embodiments still fall within the protection scope of the present invention.

[0046] In the description of the specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0047] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should fall within the protection scope of the present invention.

[0048] As described above, 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 direct current low power consumption nano-scale semiconductor electric heating diaphragm, comprising preparing a heating layer, preparing an electrode layer, and adding a heat insulating buffer layer between the heating layer and the electrode layer to form the electric heating diaphragm, characterized in that: The specific preparation steps of the DC low-power nano-scale semiconductor electric heating diaphragm are as follows: Step 1: Compounding an organic semiconductor material with nano-silver particles to form a nano-organic semiconductor ink, and spraying the nano-organic semiconductor ink onto a substrate surface by an inkjet printer to form a heating layer; Step 2: etching micro-nano grooves on the base surface of the heating layer using a mold having a groove pattern; Step 3: Use titanium, manganese dioxide and gold to sequentially deposit three materials to prepare a layered composite electrode layer, and perform interface treatment between each electronic level layer to enhance the binding force and charge transfer performance between each electronic pole layer; Step 4: using nano-organic semiconductor materials to prepare composite fibers with a hollow structure; Step 5: Using an interweaving method, two fiber bundles with different properties are interwoven to form a heat-insulating buffer layer; Step 6: Assemble the heating layer, the electrode layer and the heat-insulating buffer layer into an electric heating diaphragm, perform performance tests and quality inspections, and package qualified electric heating diaphragms; In the step 2, an electron beam lithography machine is used to draw a wavy micro-nano groove pattern on the surface of the silicon mold, the wavelength of the wave is set to 1um-10um, the amplitude is 100nm-500nm, the width of the groove is set to 50nm-500nm, the depth is set to 100nm-1000nm, the spacing between adjacent grooves is set to 200nm-1000nm, the acceleration voltage of the electron beam lithography machine is set to 5kV-30kV, the beam current is set to 1nA-10nA, and the silicon mold with the micro-nano groove pattern is placed on the surface of the heating layer material, and placed in a hot stamping device, and stamped at a temperature of 100℃-150℃ and a pressure of 50MPa-100MPa for 5min-10min. After the stamping is completed, the groove pattern is transferred to the heating layer material using oxygen plasma, the etching power is set to 50W-200W, the air pressure is set to 0.5Pa-5Pa, and the etching time is 10min-60min, and a wavy micro-nano groove pattern is etched on the surface of the heating layer; In the step three, titanium is used as the bottom layer in the composite electrode layer, a titanium layer with a thickness of 10nm-100nm is deposited on the substrate by magnetron sputtering technology, hydroxyl groups are introduced on the surface of the titanium layer by chemical adsorption, the substrate with the titanium layer is immersed in a solution containing hydrogen peroxide and sodium hydroxide, and the reaction is carried out at a temperature of 40°C-60°C for 30min-60min to form a hydroxylated surface layer on the surface of the titanium layer, and then the substrate is transferred to a solution containing manganese ions, and manganese ions are adsorbed on the surface of the hydroxylated titanium layer through Ti-O-Mn chemical bonds, and manganese dioxide is used as the composite electrode layer. The middle layer in the composite electrode layer is prepared by chemical deposition on the surface of the bottom layer to deposit manganese dioxide with a thickness of 100nm-500nm. The substrate is placed in a plasma treatment device, oxygen is introduced as a reaction gas, the radio frequency power is adjusted between 50W-200W, and the treatment time is 5min-30min. The oxygen plasma generates oxygen free radicals and peroxy free radicals on the surface of manganese dioxide. Gold is used as the top layer in the composite electrode layer, and a gold layer with a thickness of 50nm-200nm is deposited on the middle layer by magnetron sputtering technology to prepare the electrode layer in the electric heating membrane.

2. A DC low-power nano-scale semiconductor electric heating diaphragm according to claim 1, characterized in that: In the step 1, nanosilver particles are dispersed in a sodium dodecyl sulfate solution to prepare a nanosilver particle dispersion, wherein the concentration of the sodium dodecyl sulfate is set to 1%-5% of the mass of the nanosilver particles, a 3-hexylthiophene monomer with a purity of 99% is prepared, and the 3-hexylthiophene monomer is dissolved in anhydrous chloroform under nitrogen protection to prepare a 0.1 mol / L-0.5 mol / L solution, and then a ferric chloride initiator is added to the solution, wherein the molar ratio of ferric chloride to 3-hexylthiophene monomer is set to 0.01-0.1, and the solution is stirred at a temperature of 0° C.-5° C. at a rate of 60 r / min-100 r / min for 24 h-48 h to obtain a mixed solution, and then the nanosilver particle dispersion is added to the mixed solution, and an ultrasonic disperser is used to disperse the solution at a frequency of 30 kHz-50 kHz for 30 min-60 min to obtain a nano-organic semiconductor ink.

3. A DC low power consumption nano-scale semiconductor electric heating film according to claim 2, characterized in that: In the step 1, a polyimide polymer is used as a base material of the electric heating diaphragm, a nano-organic semiconductor ink is loaded into an ink cartridge of an inkjet printer, and a nozzle is used to spray the nano-organic semiconductor ink on the surface of the substrate to form a pattern. The spray frequency of the nozzle is set to 1kHz-10kHz, and the distance between the nozzle and the substrate is set to 0.1mm-1mm. The nano-organic semiconductor ink with a thickness of 100um-500um is sprayed on the surface of the substrate, and the substrate sprayed with the nano-organic semiconductor ink is added to a drying oven for drying. The drying temperature is set to 60°C-100°C, and the drying time is set to 10min-30min to form a heating layer in the electric heating diaphragm.

4. A DC low power consumption nano-scale semiconductor electric heating film according to claim 1, characterized in that: In step 4, 4,4 、 -diaminodiphenyl ether was dissolved in N-methyl-2-pyrrolidone solution to prepare diamine solution, 4,4 、 The concentration of diaminodiphenyl ether is set to 0.1mol / L-0.5mol / L, and then pyromellitic dianhydride is added to the diamine solution, and the molar ratio of diamine to dianhydride is set to 1:

1. The mixed solution is added to an electric stirrer and stirred at a temperature of 0℃-5℃ at a rate of 60r / min-100r / min for 4h-8h to obtain a polyamic acid solution. Boron nitride particles with a particle size of 10nm-100nm are selected, and the boron nitride particles are added to the N-methyl-2-pyrrolidone solution, and then the polyethylene is added. The polyvinyl pyrrolidone dispersant is used in an amount of 1%-5% of the mass of the boron nitride nanoparticles. The mixed solution is added into an ultrasonic disperser and dispersed for 30min-60min at a frequency of 20kHz-40kHz to obtain a boron nitride nanoparticle dispersion. The boron nitride nanoparticle dispersion is added into a polyamic acid solution to prepare an outer tube solution. The amount of boron nitride nanoparticles added is 1%-10% of the mass of the polyamic acid. Polyvinyl alcohol is dissolved in water to prepare an inner tube solution with a concentration of 5%-10%.

5. A DC low power consumption nano-scale semiconductor electric heating film according to claim 4, characterized in that: In the step 4, the inner tube solution is added to the inner tube of the coaxial co-spinning device, and the outer tube solution is added to the outer tube of the coaxial co-spinning device, the flow rate of the inner tube solution is set to 0.1mL / h-0.5mL / h, the flow rate of the outer tube solution is set to 0.5mL / h-2mL / h, the spinning voltage is set to 10kV-30kV, the distance between the spinneret and the receiving device is set to 10cm-30cm, the spinning device is turned on to spray the inner tube solution and the outer tube solution from the concentric spinneret at the same time to form a composite fiber with a diameter of 10um-100um, and the composite fiber is received The fibers are gathered on the device to form fiber felt, and the collected fiber felt is put into an oven for thermal imidization treatment. First, it is kept at a temperature of 100°C-150°C for 1h-2h, and then the temperature is increased to 200°C-300°C at a rate of 2°C / min-5°C / min and kept for 2h-4h to imidize the polyamic acid and solidify the fiber structure at the same time. The solidified fiber is then immersed in water at a temperature of 40°C-60°C for 1h-2h to dissolve the polyvinyl alcohol and seep out of the fiber, leaving a hollow pipe structure, to prepare a polyimide fiber with a hollow structure.

6. A DC low-power nano-scale semiconductor electric heating film according to claim 5, characterized in that: In the step 5, the polyimide fiber is made into a fiber bundle with a linear density of 10tex-100tex, and the T700 model carbon fiber is made into a fiber bundle with a linear density of 5tex-80tex, the mass ratio of polyimide fiber to carbon fiber is 3:1, and the prepared polyimide fiber bundle and carbon fiber bundle are respectively placed in two feeding devices of the air interlacing machine, and the air flow pressure of the air interlacing machine is set to 0.1MPa-0.5MPa, and the air flow rate is set to 10m 3 / h-50m 3 / h, the nozzle angle is set to 30°-60°, the feeding speed is set to 10m / min-50m / min, under the action of air flow pressure and flow, the two fiber bundles are blown away and mixed with each other in the interweaving area, and the interwoven fiber fabric is put into the heat setting equipment and treated at a temperature of 180℃-250℃ for 1min-5min to form the heat insulation buffer layer in the electric heating diaphragm.

7. A DC low-power nano-scale semiconductor electric heating diaphragm according to claim 6, characterized in that: In the step six, the heating layer and the electrode layer are added to an ultrasonic cleaning machine, ethanol is selected as an ultrasonic cleaning liquid, dust and trace impurities on the surfaces of the heating layer and the electrode layer are removed, loose fibers and dust on the surface of the fiber fabric of the thermal insulation buffer layer are removed by compressed air, a wire is welded at the lead-out end of the electrode layer, and the welding part is encapsulated and protected with insulating glue after welding, epoxy resin is coated along the edge of the electric heating diaphragm to form a closed frame with a width of 2mm-10mm, the heating layer, the electrode layer and the thermal insulation buffer layer are fixed together, the dislocation, wrinkles and protrusions between the layers of the assembled electric heating diaphragm are checked, an insulation resistance tester is used to detect the resistance value between the electrode layers, the insulation resistance between the electrode layer and the heating layer, and between the electrode layer and the external package, the surface of the electric heating diaphragm that has passed the test is cleaned and placed on antistatic polyethylene foam, the electric heating diaphragm wrapped with protective material is placed in an aluminum foil composite film, and the edges of the aluminum foil composite film are heat-sealed using a heat sealing machine, the heat sealing temperature is set to 120°C-180°C, and the heat sealing width is set to 5mm-10mm.

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