WO2020199354A1 - Fibre électrothermique résistante aux températures élevées et son application - Google Patents

Fibre électrothermique résistante aux températures élevées et son application Download PDF

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WO2020199354A1
WO2020199354A1 PCT/CN2019/091445 CN2019091445W WO2020199354A1 WO 2020199354 A1 WO2020199354 A1 WO 2020199354A1 CN 2019091445 W CN2019091445 W CN 2019091445W WO 2020199354 A1 WO2020199354 A1 WO 2020199354A1
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fiber
temperature resistant
electric heating
high temperature
resistant electric
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PCT/CN2019/091445
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English (en)
Chinese (zh)
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李辰宇
汪威
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碳翁(北京)科技有限公司
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • the invention belongs to the field of materials, and specifically relates to a high-temperature resistant electric heating fiber and its application in the field of electric heating components.
  • Electric heating materials are used in the manufacture of heating elements in various resistance heating equipment. At present, the electric heating method has been widely used because of its advantages such as easy control and adjustment, no pollution to the environment, and good product quality. Among them, the resistance heating method using the resistance heating element as the electrothermal conversion medium is the most convenient and widely used.
  • Common electric heating materials include metal electric heating materials and non-metal electric heating materials. The main disadvantage of metal electric heating materials is that they are expensive and demanding on the conditions of use. Among them, refractory metal electric heating materials must be used in a vacuum or protective atmosphere. Metallic electric heating materials are usually processed into a wire spiral or wave structure, which is prone to inductive reactance effect and energy loss when energized.
  • non-metallic electric heating materials Compared with metal electric heating materials, non-metallic electric heating materials have the advantages of high temperature resistance, corrosion resistance, oxidation resistance, and high electrothermal conversion efficiency. No matter in the field of high temperature heating or medium and low temperature heating, non-metallic electric heating materials are gradually replacing metal electric heating materials.
  • non-metallic heating elements are generally processed into rods, strips, plates, or U shapes through biscuit and sintering processes, which cannot solve the problems of large resistance dispersion and poor mechanical properties. Therefore, the research and development of new high-performance electric heating materials not only has important scientific research significance, but also has important practical application value.
  • the purpose of the present invention is to provide a high-temperature resistant electric heating fiber material.
  • the electric heating material of the present invention is prepared by a method of directly growing microcrystalline graphite, and the performance of the electric heating material is greatly optimized and the cost is greatly reduced.
  • Microcrystalline graphite is a carbon nanomaterial in which hexagonal carbon atoms composed of sp 2 hybrid orbitals are randomly distributed on the substrate in a honeycomb lattice to form a disordered superstructure.
  • the infrared emissivity of the electrothermal fiber prepared by the invention is as high as 0.95, which can effectively improve the heat conversion rate and reduce the power consumption; it has outstanding advantages such as high temperature resistance, flexibility, easy configuration, and adjustable resistivity, and has low thermal inertia and is heated The advantages of close body contact and low heat conduction loss.
  • the range of use of traditional electric heating materials can be expanded, making it used in many fields such as household appliances, electronics, medical treatment, transportation, and aerospace.
  • the present invention provides a high temperature resistant electric heating fiber
  • the high temperature resistant electric heating fiber includes a fiber inner core and a microcrystalline graphite layer covering the fiber inner core, and the fiber inner core adopts High temperature fiber.
  • the microcrystalline graphite layer is deposited on the surface of the fiber inner core by a chemical vapor deposition method.
  • the thickness of the microcrystalline graphite layer is less than 10 microns.
  • the microcrystalline graphite layer is wrapped outside the fiber layer in the following manner:
  • Step 1 Prepare insulating fiber material
  • Step 2 Perform surface coating treatment on the fiber material, and the coating layer contains a carbon source cracking catalytic material (a material that has a catalytic cracking effect on the carbon source);
  • Step 3 Place the coated fiber material in a vacuum reaction chamber
  • Step 4 Pass protective gas and reducing gas into the vacuum reaction chamber, and then pass in a carbon source to grow microcrystalline graphite;
  • Step 5 cooling the fiber material under a protective gas and reducing gas atmosphere to obtain a high-temperature resistant electric heating fiber.
  • the fiber material is a clean fiber material.
  • the carbon source cracking catalytic material is a metal carbon source cracking catalytic material.
  • the carbon source cracking catalytic material has volatility under low pressure (for example, less than 100 Pa).
  • the carbon source cracking catalytic material is a volatile material under reaction temperature and low pressure conditions.
  • the growth time of the microcrystalline graphite is controlled after the attached film layer is completely volatilized, for example, after the volatilization amount of the film layer exceeds 99.9%.
  • the fiber material is selected from at least one of a single fiber, a single fiber, and a fiber cloth.
  • the carbon source cracking catalytic material is a metal carbon source cracking catalytic material, and preferably, the catalytic material is a nano-scale metal material.
  • the thickness of the film layer is 10-100 ⁇ m, preferably less than 60 ⁇ m.
  • the present invention provides an electrical appliance with a heating source, characterized in that the electrical appliance comprises a power source, at least two electrodes, and the high-temperature resistant electric heating fiber of claim 1, and the power source is respectively connected to the two electrodes ,
  • the electrodes are respectively electrically connected with different parts of the high temperature resistant electric heating fiber.
  • the present invention provides a method for preparing a high temperature resistant electric heating fiber, the method comprising:
  • Step 1 Prepare insulating fiber material
  • Step 2 Perform surface coating treatment on the fiber material, and the coating layer contains a carbon source cracking catalytic material;
  • Step 3 Place the coated fiber material in a vacuum reaction chamber
  • Step 4 Pass protective gas and reducing gas into the vacuum reaction chamber, and then pass in a carbon source to grow microcrystalline graphite;
  • Step 5 cooling the fiber material under a protective gas and reducing gas atmosphere to obtain a high-temperature resistant electric heating fiber.
  • the present invention provides an application of the high temperature resistant electric heating fiber.
  • the application includes applying a voltage across the high temperature resistant electric heating fiber to perform electrothermal conversion.
  • the application includes The high temperature resistant electric heating fiber is used in the high temperature environment with or producing 200-1200 degrees Celsius, and the infrared radiation is the main method for electrothermal conversion.
  • the present invention provides a high temperature resistant electric heating fiber cloth, characterized in that the high temperature resistant electric heating fiber cloth includes a fiber core woven by high temperature resistant insulating fibers and microcrystalline graphite coated on the fiber core Floor.
  • the thickness of the coated film layer is 10-100 ⁇ m, more preferably 40-60 ⁇ m.
  • the protective gas includes an inert gas
  • the reducing gas includes H2
  • the step 4 further includes the step of introducing a carbon source after the gas flow of the protective gas and the reducing gas is stabilized.
  • the carbon source cracking catalytic material is a volatile material under reaction temperature and low pressure conditions.
  • the film layer is preferably a sparse structure film layer.
  • step 1 may include the process of cleaning the fibers: the fibers are sequentially placed in cyclohexane, ethanol, and deionized water for ultrasonic cleaning for a predetermined time, such as 10 minutes, and dried with nitrogen to complete the cleaning of the fibers.
  • the fiber may be selected from at least one of high-temperature resistant quartz fiber, glass fiber, asbestos fiber, metal fiber, nitrile boron fiber, ceramic fiber, and other fibers that can be used above 300°C. That is, the selected fibers are all insulating and heat-resistant fiber materials.
  • the metal coating process is preferably performed through a metal coating process, and the thickness of the metal film is not greater than 100 ⁇ m.
  • the coating metal is selected from at least one of metals that can catalyze the cracking of carbon sources, such as copper, nickel, and platinum.
  • the attached film layer needs to meet the temperature conditions of 300°C-1100°C and the pressure conditions during the reaction in step 4 to have a volatilization effect.
  • the metal coating process is selected from at least one of electroplating, electroless plating, sol-gel, magnetron sputtering, and direct spraying of the metal coating, preferably a direct spraying method of nano metal particles.
  • the flow into the reaction chamber can be 800-1000sccm Ar and 800-1000sccm H2.
  • the growth time can be controlled within 10-300 minutes, preferably 40-300 minutes, and the growth process is set at 300°C-1100°C, thereby forming a microcrystalline graphite layer with a controllable thickness on the surface of the metal-clad fiber.
  • the carbon source is selected from gaseous (methane, ethylene, acetylene), solid (polyaniline, polystyrene, etc.), liquid (toluene, benzoic acid, chlorobenzene, ethanol, acetonitrile, etc.) carbon sources At least one.
  • Step 5 specifically includes: after the growth of microcrystalline graphite, turn off the carbon source vapor, set the flow distribution of Ar and H2 to 100-300sccm/100-300sccm, start the cooling process, turn off Ar/H2 after the temperature drops to room temperature, and take out the sample , Complete the entire preparation process.
  • reaction temperature various gas flow rates, and reaction time involved in the above preparation process can be adjusted according to process requirements.
  • the applicant of the present application finally obtained a high infrared emissivity, low surface resistance value, high temperature resistance electric heating fiber, which can achieve high temperature resistance of 1200 degrees and realize the surface
  • the resistance value is lower than 100 ⁇ /sq (even as low as 10 ⁇ /sq in Example 1), and the infrared radiation rate is higher than 90%, basically reaching more than 95% (corresponding to the best embodiment of the present invention).
  • the electrothermal fiber obtained by other methods cannot achieve such excellent performance in all aspects. For example, the use of magnetron sputtering to spray copper will result in a significant decrease in electrical performance.
  • the middle fiber filament is covered with microcrystalline graphite, not only the toughness and air permeability of the electric heating fiber can be increased, but also the heat radiation area can be increased, and the heat conversion efficiency can be further improved. % Of electrothermal conversion efficiency.
  • the method of the present invention has low cost, high yield, and the prepared electrothermal fiber has excellent properties such as good hydrophobicity and air permeability, and has huge social and economic value.
  • the electrothermal fiber material of the sub-optimal embodiment of the present invention can withstand high temperatures above 500 degrees and the infrared radiation rate can reach 80%.
  • Figure 1 is a schematic diagram of a chemical vapor deposition (CVD) system.
  • Example 2 is a physical diagram of the high-temperature electric heating fiber cloth prepared in Example 1.
  • Example 3 is an SEM image of the electric heating fiber cloth prepared in Example 1.
  • Example 4 is an electrothermal diagram of the electrothermal fiber cloth prepared in Example 1.
  • 5 and 6 are diagrams showing the hydrophobic properties of the surface of the electrothermal fiber cloth prepared in Example 1.
  • Example 7 is a diagram showing the surface air permeability characteristics of the electric heating fiber cloth prepared in Example 1.
  • Example 8 is a graph showing the electrothermal performance of the electrothermal fiber cloth and the metal wire electrothermal film prepared in Example 6.
  • Figure 1 shows a conventional chemical vapor deposition equipment, and the high temperature resistant fiber of the present invention can be realized by using this equipment.
  • the equipment mainly includes a gas supply part on the left, a high temperature tube furnace in the middle, and a cooling and gas exhaust device on the right.
  • the gas supply part is used to provide protective gas, reducing gas and carbon source to the high-temperature tube furnace.
  • the high-temperature tube furnace is the main reaction equipment in which microcrystalline graphite is grown, and the gas exhaust device is used to react the remaining gas. Processing.
  • the high temperature resistant electric heating fiber of the present invention includes a fiber inner core and a microcrystalline graphite layer covering the fiber inner core.
  • the following describes in detail an exemplary process of coating microcrystalline graphite with fibers as the inner core.
  • the quartz fiber cloth is cleaned by ultrasonic cleaning, and copper is sprayed at room temperature (for example, 20% of the mass fraction of nano copper powder (Aladdin-C103844) is ultrasonically dispersed in the ethanol solution to form a mixed solution.
  • room temperature for example, 20% of the mass fraction of nano copper powder (Aladdin-C103844) is ultrasonically dispersed in the ethanol solution to form a mixed solution.
  • an ordinary paint spray gun that is The advanced technology that can directly spray the metal coating. This is the existing technology, which will not be described in detail here.
  • the method of covering the surface of the quartz fiber with copper to form a copper sparse structure film (the same below), and controlling the thickness of the copper film to 50 ⁇ m ( Therefore, there is no metal residue in the subsequent reaction process, and the applicant found that once there is catalyst residue in the fiber, the fiber will be easy to age and break).
  • the copper-clad quartz fiber cloth into a 3-inch diameter high-temperature tube furnace at 1100°C, and use an oil-free scroll vacuum pump to pump the pressure in the reaction chamber in the high-temperature tube furnace below 100 Pa, preferably 10 Pa below, the flow of Ar/H 2 is controlled to 1000/1000sccm.
  • the toluene gas valve is opened into the reaction chamber, and toluene gas is introduced into the reaction chamber. The flow is controlled to 1000sccm. The toluene vapor enters the reaction chamber quickly.
  • the carbon material growth process was set to 120 minutes, and the toluene valve was quickly closed after the growth was completed, and the Ar/H 2 was set to 300/300 sccm to start the cooling process.
  • the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
  • the flow rates of the carbon source, the protective gas, and the reducing gas can be appropriately adjusted as needed, and the values in the embodiment are not necessarily limited.
  • the flow of Ar/H 2 in the early stage can be controlled to 700-1300 sccm; after the growth, the Ar/H 2 can be set to 200-500.
  • the sample By applying 3V DC/AC, the sample can be heated to 100°C in an instant (less than 1 second), showing good rapid heating characteristics and uniform heating surface; JCY-2 The drop contact angle measuring instrument measured the contact angle of the fiber cloth to be 100 degrees, showing the characteristics of hydrophobicity; comparing the sample before and after in a water vapor environment at 100°C, it can be seen that the sample has good air permeability characteristics.
  • the surface of the sample to be tested receives the infrared radiation radiated by a 100°C hemispherical black body, and then receives the infrared radiation reflected by the sample, measures the infrared radiation reflectivity and obtains the sample according to the calibration value (Electrothermal fiber cloth) infrared emissivity, the measurement result is that the infrared emissivity is 0.95.
  • the German Bruker X-ray energy spectrometer (QUANTAX EDS) system to analyze the types of elements in the sample micro-area, no residual Cu element was detected.
  • the electrothermal conversion efficiency is close to 100%, and can reach more than 99%.
  • the high temperature resistance of 1200°C (the same below) or other temperatures mentioned in the fire resistance test mentioned in the present invention is not an absolute limit for embrittlement, but only when the test is carried out to the vicinity of this temperature. When the temperature is raised, obvious embrittlement will be found. The description of this temperature is only used to prove the approximate degree of the high temperature resistance of the product of the present invention.
  • a large amount of activated carbon material is adsorbed on the surface of the quartz fiber, migrates and collides on the surface, thereby realizing the nucleation and growth of microcrystalline graphite.
  • the carbon material growth process is set to 120 minutes. After the growth is completed, the toluene valve is quickly closed, and the Ar/H 2 flow rate is controlled to 300/300sccm, and the cooling process is started. When the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
  • the surface of the sample to be tested receives the infrared radiation radiated by a 100°C hemispherical black body, and the infrared radiation reflected by the sample is received.
  • the infrared reflectance is measured and the infrared radiation of the sample is obtained according to the calibration value.
  • the measurement result is that the infrared emissivity is 0.86, which is somewhat lower than the structure in Example 1.
  • the German Bruker X-ray energy spectrometer (QUANTAX EDS) system was used to analyze the types of elements in the sample micro-regions, and a small amount of Cu element residue was detected.
  • the applicant found that the metal copper film obtained by magnetron sputtering has a greater bonding force with the fiber surface.
  • the metal copper film obtained by magnetron sputtering has a greater bonding force with the fiber surface.
  • Metal copper is easily oxidized under high temperature conditions in the air, which causes the heat resistance temperature of the sample to drop.
  • the infrared emissivity of metallic copper is much lower than that of microcrystalline graphite, so the infrared emissivity of sample 2 appears to decrease.
  • the quartz fiber cloth is cleaned by ultrasonic cleaning, nickel is coated on the surface of the quartz fiber by spraying nickel at room temperature, and the thickness of the nickel film is controlled to 30 ⁇ m; the nickel-coated quartz fiber is placed in a high temperature tube furnace at 400°C,
  • the oil scroll vacuum pump pumps the pressure in the reaction chamber to below 10Pa, and the flow of Ar/H 2 is controlled to 1000/1000sccm through the reaction chamber.
  • the gas flow is stable, open the ethylene gas valve and feed ethylene into the reaction chamber to control the flow At 1000sccm, the ethylene gas quickly cracks into activated carbon material after entering the reaction chamber.
  • a large amount of activated carbon material is adsorbed on the surface of the quartz fiber, migrates and collides on the surface, so as to realize the nucleation and growth of microcrystalline graphite.
  • the carbon material growth process is set to 120 minutes. After the growth is completed, the ethylene valve is quickly closed, and the Ar/H 2 flow rate is controlled to 300/300sccm, and the cooling process is started. When the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
  • Perform performance test on the obtained sample use a liquefied gas torch to conduct a heat resistance test on the prepared electrothermal fiber.
  • the test result is that when the temperature is greater than 1200°C, the fiber begins to crack and has non-combustible characteristics; four probes are used The tester tests the sample 3, and the test result is that the surface resistance value is 100 ⁇ /sq.
  • the surface of the sample to be tested receives the infrared radiation radiated by a 100°C hemispherical black body, and the infrared radiation reflected by the sample 3 is received, the infrared reflectance is measured and the infrared of the sample is obtained according to the calibration value Radiation emissivity, the measurement result is that the infrared emissivity is 0.96.
  • the German Bruker X-ray energy spectrometer (QUANTAX EDS) system to analyze the types of elements in the sample micro-area, no nickel residues were detected. Compared with Example 1, the growth temperature is greatly reduced.
  • the carbon source is formed by catalytic cracking on the surface of nickel under high temperature conditions. Atoms or carbon radicals will enter the bulk phase of the nickel metal substrate, and then precipitate from the bulk nickel metal phase to the surface to form a thicker microcrystalline graphite layer when the temperature is lowered.
  • the quartz fiber cloth is cleaned by ultrasonic cleaning, nickel is coated on the surface of the quartz fiber by spraying nickel at room temperature, and the thickness of the nickel film is controlled to 30 ⁇ m; the nickel-coated quartz fiber is placed in a high-temperature tube furnace at 300°C, The oil vortex vacuum pump pumps the pressure in the reaction chamber to below 10Pa, and the flow of Ar/H 2 is controlled to 1000/1000sccm into the reaction chamber.
  • the toluene gas quickly cracks into activated carbon material after entering the reaction chamber, and a large amount of activated carbon material is adsorbed on the surface of the quartz fiber, migrates and collides on the surface, thereby realizing the nucleation and growth of microcrystalline graphite.
  • the carbon material growth process is set to 120 minutes.
  • the toluene valve is quickly closed, and the Ar/H 2 flow rate is controlled to 300/300sccm, and the cooling process is started.
  • the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
  • the measurement result is , Infrared emissivity is 0.96.
  • QUANTAX EDS German Bruker X-ray energy spectrometer
  • the growth temperature is reduced to 300°. Analysis shows that by controlling toluene under the condition of nickel metal catalysis, low-temperature cracking can be achieved, and there are a large number of benzene ring radicals, which can achieve hexagonal honeycomb carbon crystals. The grid stacks quickly.
  • the quartz fiber cloth is cleaned by ultrasonic cleaning, nickel is coated on the surface of the quartz fiber by spraying nickel at room temperature, and the thickness of the nickel film is controlled to 10 ⁇ m; the nickel-coated quartz fiber is placed in a high temperature tube furnace at 400°C,
  • the oil vortex vacuum pump pumps the pressure in the reaction chamber to below 10Pa, and the flow of Ar/H 2 is controlled to 1000/1000sccm into the reaction chamber.
  • the toluene gas quickly cracks into activated carbon material after entering the reaction chamber, and a large amount of activated carbon material is adsorbed on the surface of the quartz fiber, migrates and collides on the surface, thereby realizing the nucleation and growth of microcrystalline graphite.
  • the carbon material growth process is set to 20 minutes, and the toluene valve is quickly closed after the growth is completed, and the Ar/H 2 flow rate is controlled to 300/300 sccm, and the cooling process is started.
  • the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
  • Perform performance test on the obtained sample use a liquefied gas torch to conduct a heat resistance test on the prepared electrothermal fiber.
  • the test result is that when the temperature is greater than 1200°C, the fiber begins to crack and has non-combustible characteristics; four probes are used
  • the tester tests the sample, and the test result is that the surface resistance value is 1800 ⁇ /sq.
  • the surface of the sample to be tested receives the infrared radiation radiated by a 100°C hemispherical black body, and the infrared radiation reflected by the sample is received. The infrared reflectance is measured and the infrared of the sample is obtained according to the calibration value.
  • the measurement result is that the infrared emissivity is 0.96.
  • QUANTAX EDS German Bruker X-ray energy spectrometer
  • the resistance value is increased.
  • the analysis shows that the thickness of the microcrystalline graphite layer on the fiber surface can be controlled by controlling the content of the nickel metal catalyst and the growth time. The larger the thickness, the lower the resistance value.
  • the glass fiber cloth is cleaned by ultrasonic cleaning, and the surface of the glass fiber is coated with nickel by the method of spraying nickel at room temperature, and the thickness of the nickel film is controlled to 30 ⁇ m; the nickel-coated glass fiber cloth is placed in a high temperature tube furnace at 500°C,
  • the oil vortex vacuum pump pumps the pressure in the reaction chamber to below 10Pa, and the flow of Ar/H 2 is controlled to 1000/1000sccm into the reaction chamber. After the flow is stable, open the toluene gas valve, and pass the pressure into the reaction chamber to control the flow At 1000sccm, the toluene vapor quickly decomposes into activated carbon material after entering the reaction chamber.
  • a large amount of activated carbon material is adsorbed on the surface of the quartz fiber, migrates and collides on the surface, thereby realizing the nucleation and growth of microcrystalline graphite.
  • the carbon material growth process is set to 120 minutes. After the growth is completed, the toluene valve is quickly closed, and the Ar/H 2 flow rate is controlled to 300/300sccm, and the cooling process is started. When the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
  • Perform performance test on the obtained sample use a liquefied gas torch to conduct a heat resistance test on the prepared electric fiber cloth.
  • the test result is that when the temperature is greater than 700 °C, the fiber cloth begins to crack, but it still has the characteristics of non-combustibility;
  • a four-probe tester was used to test the surface resistance value of the obtained sample, and the test result was that the surface resistance value was 230 ⁇ /sq;
  • the German Bruker X-ray energy spectrometer (QUANTAX EDS) system was used to analyze the types of components in the sample’s micro area. Residual nickel is detected. Take 2*2cm metal wire electric heating film and microcrystalline graphite fiber cloth to test the electric heating performance.
  • thermoelectric conversion rate of the microcrystalline graphite fiber cloth is 91.4%, and the thermoelectric conversion rate of the metal wire electric heating film is 82.1%.
  • the quartz fiber cloth is cleaned by ultrasonic cleaning, copper is coated on the surface of the quartz fiber by spraying copper at room temperature, and the thickness of the copper film is controlled to 1 ⁇ m; the nickel-coated quartz fiber is placed in a high temperature tube furnace at 1100°C,
  • the oil scroll vacuum pump pumps the pressure in the reaction chamber to below 10Pa, and the flow of Ar/H 2 is controlled to 1000/1000sccm through the reaction chamber.
  • the gas flow is stable, open the ethylene gas valve and feed ethylene into the reaction chamber to control the flow At 1000sccm, the ethylene gas quickly cracks into activated carbon material after entering the reaction chamber.
  • a large amount of activated carbon material is adsorbed on the surface of the quartz fiber, migrates and collides on the surface, so as to realize the nucleation and growth of microcrystalline graphite.
  • the carbon material growth process is set to 120 minutes. After the growth is completed, the ethylene valve is quickly closed, and the Ar/H 2 flow rate is controlled to 300/300sccm, and the cooling process is started. When the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
  • Perform performance test on the obtained sample use a liquefied gas torch to conduct a heat resistance test on the prepared electrothermal fiber.
  • the test result is that when the temperature is greater than 1200°C, the fiber begins to crack and has non-combustible characteristics; four probes are used The tester tests the obtained samples, and the test result is that the surface resistance value is greater than 10M ⁇ /sq.
  • the surface of the sample to be tested receives the infrared radiation radiated by a 100°C hemispherical black body, and the infrared radiation reflected by the sample is received to measure the reflectivity and obtain the infrared radiation emissivity of the sample according to the calibration value ,
  • the measurement result is that the infrared emissivity is 0.48, and the infrared emissivity is greatly reduced.
  • the German Bruker X-ray energy spectrometer (QUANTAX EDS) system was used to analyze the types of components in the sample micro-area, and no copper residues were detected.
  • the analysis shows that because the thickness of the copper film is too thin, the copper volatilizes rapidly under high temperature conditions, and the copper vapor is quickly evacuated from the reaction chamber by vacuuming.
  • the concentration of copper vapor is too low to achieve an effective catalytic effect, resulting in carbon materials
  • the particles are deposited on the surface of the fiber in the form of amorphous carbon. Therefore, the resistance value of sample 7 increases sharply, and the infrared emissivity decreases greatly.
  • the quartz fiber cloth is cleaned by ultrasonic cleaning, copper is coated on the surface of the quartz fiber by spraying copper at room temperature, and the thickness of the copper film is controlled to 200 ⁇ m; the copper-clad quartz fiber is placed in a high temperature tube furnace at 1100°C,
  • the oil scroll vacuum pump pumps the pressure in the reaction chamber to below 10Pa, and the flow of Ar/H 2 is controlled to 1000/1000sccm through the reaction chamber.
  • the gas flow is stable, open the ethylene gas valve and feed ethylene into the reaction chamber to control the flow At 1000sccm, the ethylene gas quickly cracks into activated carbon material after entering the reaction chamber.
  • a large amount of activated carbon material is adsorbed on the surface of the quartz fiber, migrates and collides on the surface, so as to realize the nucleation and growth of microcrystalline graphite.
  • the carbon material growth process is set to 120 minutes. After the growth is completed, the ethylene valve is quickly closed, and the Ar/H 2 flow rate is controlled to 300/300sccm, and the cooling process is started. When the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
  • Perform performance test on the obtained sample use a liquefied gas torch to conduct a heat resistance test on the prepared electric fiber.
  • the test result is that when the temperature is greater than 600 °C, the fiber begins to crack and has non-combustible characteristics; four probes are used The tester tests the sample, and the test result is that the surface resistance is 8 ⁇ /sq.
  • the surface of the sample to be tested receives the infrared radiation radiated by a 100°C hemispherical black body, and the infrared radiation reflected by the sample is received to measure the reflectivity and obtain the infrared radiation emissivity of the sample according to the calibration value ,
  • the measurement result is that the infrared emissivity is 0.53.
  • the German Bruker X-ray energy spectrometer (QUANTAX EDS) system was used to analyze the types of constituent elements in the sample micro-area, and a large amount of copper residue was detected.
  • the analysis shows that due to the thick copper film, a large amount of copper remains during the high-temperature growth process, forming a composite material of fiber/copper/microcrystalline graphite. Therefore, the resistance value of the material and the infrared heating rate are reduced. At the same time, the increase in the thickness of the copper film also increases the production cost of the material. Therefore, under normal circumstances, the thickness of the copper film should not exceed 100 ⁇ m.

Abstract

La présente invention concerne une fibre électrothermique résistante aux températures élevées, la fibre électrothermique résistante aux températures élevées comprenant une âme interne de fibre et une couche de graphite microcristallin revêtue à l'extérieur de l'âme interne de fibre, l'âme interne de fibre utilisant une fibre résistante aux températures élevées. La couche de graphite microcristallin est déposée sur la surface de l'âme interne de fibre au moyen d'un procédé de dépôt chimique en phase vapeur et l'épaisseur de la couche de graphite microcristallin est de préférence inférieure à 10 micromètres. Comparativement aux matériaux électrothermiques en fibre de carbone, la solidité et la perméabilité à l'air de la fibre électrothermique de la présente invention peuvent être augmentées grâce à un filament de fibre intermédiaire et grâce à la structure dans laquelle le côté extérieur du filament de fibre intermédiaire est revêtu de graphite microcristallin. En outre, la zone de rayonnement thermique peut également être améliorée, ce qui permet d'améliorer encore plus l'efficacité de conversion thermique et d'obtenir une efficacité de conversion électrothermique de presque 100 %.
PCT/CN2019/091445 2019-04-04 2019-06-16 Fibre électrothermique résistante aux températures élevées et son application WO2020199354A1 (fr)

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