WO2020199353A1 - Preparation and use of high temperature resistant electrothermal fiber - Google Patents

Preparation and use of high temperature resistant electrothermal fiber Download PDF

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Publication number
WO2020199353A1
WO2020199353A1 PCT/CN2019/091444 CN2019091444W WO2020199353A1 WO 2020199353 A1 WO2020199353 A1 WO 2020199353A1 CN 2019091444 W CN2019091444 W CN 2019091444W WO 2020199353 A1 WO2020199353 A1 WO 2020199353A1
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Prior art keywords
fiber
electric heating
temperature resistant
high temperature
resistant electric
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PCT/CN2019/091444
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French (fr)
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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Publication of WO2020199353A1 publication Critical patent/WO2020199353A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/145—Carbon only, e.g. carbon black, graphite
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/40—Heating elements having the shape of rods or tubes
    • H05B3/54—Heating elements having the shape of rods or tubes flexible

Definitions

  • the invention belongs to the field of materials, and specifically relates to a method for preparing high-temperature resistant electric heating fibers by using a chemical vapor deposition technology (CVD) method and its application in the field of electric heating components.
  • CVD chemical vapor deposition technology
  • 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 electric 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 electrothermal 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 method for preparing a high-temperature resistant electrothermal fiber material.
  • the present invention prepares the electrothermal material by directly growing microcrystalline graphite, which can effectively optimize the performance of the electrothermal material and reduce the preparation cost.
  • Microcrystalline graphite is a carbon nanomaterial with a disordered structure formed by hexagonal carbon atoms composed of sp 2 hybrid orbitals and randomly distributed on the substrate in a honeycomb lattice.
  • 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 method for preparing a high-temperature resistant electric heating fiber, which is characterized in that the method includes the following steps:
  • 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 all the attached film layer is 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 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 H 2
  • the step 4 further includes the step of introducing the carbon source after the gas flow of the protective gas and the reducing gas is stabilized.
  • the present invention provides a high temperature resistant electric heating fiber, characterized in that the high temperature resistant electric heating fiber includes a fiber layer and a microcrystalline graphite layer covering the fiber layer.
  • 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;
  • 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, and the application includes applying a voltage across the high-temperature resistant electric heating fiber to perform electrothermal conversion.
  • the application includes applying the high temperature resistant electrothermal fiber to a high temperature environment with or generating 200-1200 degrees Celsius, and performing electrothermal conversion based on infrared radiation.
  • Step 1 may include a process of cleaning the fibers: sequentially placing the fibers in cyclohexane, ethanol, and deionized water, ultrasonically cleaning them for a predetermined time, such as 10 minutes, and drying 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 has discovered a method for preparing electrothermal fibers that can achieve high infrared emissivity, low surface resistance, and high temperature resistance.
  • the prepared electric heating material can achieve high temperature resistance of 1200 degrees, realize the surface resistance value is lower than 100 ⁇ /sq (even as low as 10 ⁇ /sq in embodiment 1), and the infrared radiation rate is higher than 90%, basically reaching 95% (corresponding to the present invention Best Practice).
  • the surface resistance value can be prepared Electric heating fiber with lower than 100/sq, 95% infrared radiation rate and high temperature resistance of 1200 degrees.
  • the electrothermal fiber obtained by other methods cannot achieve such excellent performance in all aspects.
  • 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.
  • an electrothermal fiber material that can withstand a high temperature of more than 500 degrees and an infrared radiation rate of more than 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 electric heating 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 method of the present invention can be implemented 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 quartz fiber cloth is cleaned by ultrasonic cleaning, and copper is sprayed at room temperature (20% of the mass fraction of nano copper powder (Aladdin-C103844) is ultrasonically dispersed in the ethanol solution to form a mixed solution, and a common paint spray gun is used , You can directly spray the advanced technology of the metal coating, this is the prior art, 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 50 ⁇ m (so that there is no metal residue in the subsequent reaction process, the applicant found that once there is catalyst residue in the fiber, the fiber will be easy to age and break).
  • 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- The two-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 100 °C water vapor environment, it can be seen that the sample has good air permeability characteristics.
  • the TIR 100-2 rapid emissivity tester is used to make the surface of the sample to be tested receive the infrared radiation radiated by a 100°C hemispherical black body, and then receive the infrared radiation reflected by the sample, measure the infrared radiation reflectivity and obtain the sample according to the calibration value ( The infrared emissivity of the heating fiber cloth), the measurement result is that the infrared emissivity is 0.95.
  • QUANTAX EDS German Bruker X-ray energy spectrometer
  • 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.
  • the toluene vapor quickly decomposes into activated carbon species after entering the reaction chamber, and a large amount of activated carbon species adsorbs to the surface of the quartz fiber, migrates and collides on the surface, thereby achieving 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 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 according to the calibration value.
  • the infrared emissivity was 0.86, which was 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.
  • 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 surface resistance value of the sample, 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 then receives the infrared radiation reflected by the sample, measures the infrared radiation reflectivity and obtains the infrared radiation according to the calibration value 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.
  • the sample prepared in this example has a much lower growth temperature than that in Example 1.
  • the carbon atoms or carbon radicals formed after catalytic cracking on the surface 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 toluene gas valve After the air flow is stable, open the toluene gas valve and pass in toluene gas to reduce the flow Controlled to 1000sccm, the toluene gas quickly decomposes into activated carbon species after entering the reaction chamber, and a large number of activated carbon species are adsorbed on the surface of the quartz fiber, migrate and collide 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.
  • the test result is that when the temperature is greater than 1200 °C, the fiber starts to appear brittle and has non-combustible characteristics. Under the following conditions, there is basically no embrittlement after 5 minutes of continuous high temperature; the surface resistance value of the sample is tested with a four-probe tester, and the test result is that the surface resistance value is 150 ⁇ /sq.
  • 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 infrared radiation according to the calibration value 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.
  • Example 3 Compared with the sample in Example 3, the growth temperature of the sample prepared in this example is lowered 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 free radicals. Realize the rapid stacking of hexagonal honeycomb carbon lattice.
  • 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 surface resistance of the sample, and the test result is that the surface resistance is 1800 ⁇ /sq.
  • 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 reflectivity and obtains the infrared radiation of the sample according to the calibration value Emissivity, the measurement result is that the infrared emissivity is 0.96.
  • the German Bruker X-ray energy spectrometer (QUANTAX EDS) system was used to analyze the types of elements in the sample micro-area, and no nickel residue was detected. Compared with the sample of Example 4, the resistance value of the sample of this example is higher.
  • the analysis shows that by controlling the content of the nickel metal catalyst and the growth time, the thickness of the microcrystalline graphite layer on the fiber surface can be controlled. The greater the thickness, the lower the resistance value. .
  • the cavity is quickly decomposed into activated carbon species, a large number of activated carbon species are adsorbed on the surface of the glass fiber, migrate and collide on the surface, so as to realize 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.
  • 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 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 surface resistance value of the sample, and the test result is that the surface resistance value is greater than 10M ⁇ /sq.
  • the surface of the tested sample receives the infrared radiation radiated by a 100°C hemispherical black body, and the infrared radiation reflected by the sample 7 is received to measure the reflectivity and obtain the infrared radiation emissivity according to the calibration value.
  • the measurement result is that the infrared emissivity is 0.48, and the infrared emissivity is greatly reduced.
  • QUANTAX EDS German Bruker X-ray energy spectrometer
  • 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.
  • 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 surface resistance of the sample, and the test result 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 8 is received to measure the reflectivity and obtain the infrared radiation emission 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.

Abstract

Provided are the preparation and use of a high temperature resistant electrothermal fiber. The method comprises: step 1: preparing an insulating fiber material; step 2: subjecting the fiber material to a surface coating treatment, wherein the coated film layer comprises a material from the catalytic pyrolysis of a carbon source; step 3: placing the coated fiber material in a vacuum reaction chamber; step 4: introducing an inert gas and H2 into the vacuum reaction chamber, and introducing the carbon source after the gas flow is stable to grow microcrystalline graphite; and step 5: cooling the fiber material in the atmosphere of the inert gas and H2, so as to obtain the high temperature resistant electrothermal fiber.

Description

一种耐高温电热纤维的制备与应用Preparation and application of a high temperature resistant electric heating fiber
相关申请Related application
本申请主张于2019年4月4日提交的、名称为“一种耐高温电热纤维的制备与应用”的中国发明专利申请：2019102727494的优先权。This application claims the priority of the Chinese invention patent application: 2019102727494 filed on April 4, 2019 and titled "Preparation and Application of a High Temperature Resistance Electrothermal Fiber".
技术领域Technical field
本发明属于材料领域，具体涉及一种利用化学气相沉积技术(CVD)法制备耐高温电热纤维的方法及其在电热元器件领域的应用。The invention belongs to the field of materials, and specifically relates to a method for preparing high-temperature resistant electric heating fibers by using a chemical vapor deposition technology (CVD) method and its application in the field of electric heating components.
背景技术Background technique
随着航空航天、电子电工、冶金化工、交通、汽车、军工等行业的飞速发展，对材料的热加工成形及热处理条件要求越来越严格。因此，加热方式和新型加热材料的开发研究已经成为材料科学和能源开发领域的研究热点。With the rapid development of aerospace, electronics and electrical engineering, metallurgy and chemical industry, transportation, automobile, military industry and other industries, the requirements for the thermal processing and heat treatment conditions of materials are becoming more and more stringent. Therefore, the development and research of heating methods and new heating materials have become research hotspots in the fields of materials science and energy development.
电热材料是用于制造各种电阻加热设备中的发热元件。目前，电加热方式因具有易于控制和调节且不污染环境、有利于提高产品质量等优点而得到了广泛的应用。其中以电阻加热元件作为电热转换媒介的电阻式加热方式最为简便和应用广泛。常见的电热材料包括金属电热材料和非金属电热材料两类。金属电热材料的主要缺点是价格昂贵，对使用条件要求苛刻，其中，难熔金属电热材料必须在真空或保护气氛中使用。金属类电热材料通常被加工成线材螺旋形或波形结构，通电时容易产生感抗效应造成能量损耗。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.
非金属电热材料与金属电热材料相比具有耐高温、耐腐蚀、抗氧化、电热转换效率高等优点，无论是高温加热领域还是中低温加热领域，非金属电热材料正在逐步取代金属电热材料。然而，非金属电热元件一般通过素烧工艺和烧结工艺，被加工成棒状、条状、板状或U形等，无 法解决元件电阻离散性大和力学性能差等问题。因此，研究和开发新型高性能电热材料不仅具有重要的科学研究意义，更具有重要的实际应用价值。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. However, non-metallic electric 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 electrothermal materials not only has important scientific research significance, but also has important practical application value.
发明内容Summary of the invention
本发明目的在于提供一种耐高温的电热纤维材料的制备方法，本发明通过直接生长微晶石墨的方法制备电热材料，该方法能够有效优化电热材料的性能并降低制备成本。微晶石墨是碳原子以sp 2杂化轨道所组成的六角型呈蜂巢晶格无规则的分布在基底上，所形成的无序结构的碳纳米材料。本发明制备出的电热纤维的红外发射率高达0.95，能有效提高热转换率，降低电能消耗；具有耐高温、柔性、易构型及电阻率可调等突出优势，热惯性小，与被加热体接触较密切、热传导损失小等优点。可扩展传统电热材料的使用范围，使其应用在如家用电器、电子、医疗、交通、宇航等众多领域。 The purpose of the present invention is to provide a method for preparing a high-temperature resistant electrothermal fiber material. The present invention prepares the electrothermal material by directly growing microcrystalline graphite, which can effectively optimize the performance of the electrothermal material and reduce the preparation cost. Microcrystalline graphite is a carbon nanomaterial with a disordered structure formed by hexagonal carbon atoms composed of sp 2 hybrid orbitals and randomly distributed on the substrate in a honeycomb lattice. 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.
具体而言，第一方面，本发明提供一种耐高温电热纤维的制备方法，其特征在于，所述方法包括下述步骤：Specifically, in the first aspect, the present invention provides a method for preparing a high-temperature resistant electric heating fiber, which is characterized in that the method includes the following steps:
步骤1：准备绝缘的纤维材料；Step 1: Prepare insulating fiber material;
步骤2：对所述纤维材料进行表面覆膜处理，所覆的膜层包含碳源裂解催化材料(对碳源具有催化裂解作用的材料)；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);
步骤3：将覆膜后的所述纤维材料置于真空反应腔中；Step 3: Place the coated fiber material in a vacuum reaction chamber;
步骤4：向所述真空反应腔中通入保护气体和还原性气体，然后通入碳源，进行微晶石墨生长；Step 4: Pass protective gas and reducing gas into the vacuum reaction chamber, and then pass in a carbon source to grow microcrystalline graphite;
步骤5：在保护气体和还原性气体氛围下，对所述纤维材料进行降温，获得耐高温电热纤维。Step 5: cooling the fiber material under a protective gas and reducing gas atmosphere to obtain a high-temperature resistant electric heating fiber.
优选地，所述纤维材料为清洁纤维材料。Preferably, the fiber material is a clean fiber material.
优选地，所述碳源裂解催化材料为金属碳源裂解催化材料。优选地，所述碳源裂解催化材料在低压下(比如低于100Pa)具有挥发性。优选地，所述碳源裂解催化材料为在反应温度和低压条件下的挥发性材料。Preferably, the carbon source cracking catalytic material is a metal carbon source cracking catalytic material. Preferably, the carbon source cracking catalytic material has volatility under low pressure (for example, less than 100 Pa). Preferably, the carbon source cracking catalytic material is a volatile material under reaction temperature and low pressure conditions.
优选地，在所述步骤4中微晶石墨的生长时间控制在所附膜层全部 挥发之后，比如，所覆膜层挥发量超过99.9％之后。Preferably, in the step 4, the growth time of the microcrystalline graphite is controlled after all the attached film layer is volatilized, for example, after the volatilization amount of the film layer exceeds 99.9%.
优选地，所述纤维材料选自单根纤维、单束纤维、纤维布中的至少一种。Preferably, the fiber material is selected from at least one of a single fiber, a single fiber, and a fiber cloth.
优选地，所覆膜层的厚度为10-100μm，更优选为40-60μm。Preferably, the thickness of the coated film layer is 10-100 μm, more preferably 40-60 μm.
优选地，所述保护气体包括惰性气体，所述还原性气体包括H 2，所述步骤4还包括待保护气体和还原性气体的气流稳定后，再通入碳源。 Preferably, the protective gas includes an inert gas, and the reducing gas includes H 2 , and the step 4 further includes the step of introducing the carbon source after the gas flow of the protective gas and the reducing gas is stabilized.
另一方面，本发明提供一种耐高温电热纤维，其特征在于，所述耐高温电热纤维包括纤维层和包覆在所述纤维层外的微晶石墨层。On the other hand, the present invention provides a high temperature resistant electric heating fiber, characterized in that the high temperature resistant electric heating fiber includes a fiber layer and a microcrystalline graphite layer covering the fiber layer.
优选地，所述微晶石墨层通过下述方式包覆在所述纤维层外：Preferably, the microcrystalline graphite layer is wrapped outside the fiber layer in the following manner:
步骤1：准备绝缘的纤维材料；Step 1: Prepare insulating fiber material;
步骤2：对所述纤维材料进行表面覆膜处理，所覆的膜层包含碳源裂解催化材料；Step 2: Perform surface coating treatment on the fiber material, and the coating layer contains a carbon source cracking catalytic material;
步骤3：将覆膜后的所述纤维材料置于真空反应腔中；Step 3: Place the coated fiber material in a vacuum reaction chamber;
步骤4：向所述真空反应腔中通入保护气体和还原性气体，然后通入碳源，进行微晶石墨生长；Step 4: Pass protective gas and reducing gas into the vacuum reaction chamber, and then pass in a carbon source to grow microcrystalline graphite;
步骤5：在保护气体和还原性气体氛围下，对所述纤维材料进行降温，获得耐高温电热纤维。Step 5: cooling the fiber material under a protective gas and reducing gas atmosphere to obtain a high-temperature resistant electric heating fiber.
另一方面，本发明提供一种所述耐高温电热纤维的应用，所述应用包括在所述耐高温电热纤维两端施加电压，以进行电热转换。In another aspect, the present invention provides an application of the high-temperature resistant electric heating fiber, and the application includes applying a voltage across the high-temperature resistant electric heating fiber to perform electrothermal conversion.
优选地，所述应用包括将所述耐高温电热纤维应用于具有或产生200-1200摄氏度的高温环境中，以红外辐射为主的方式进行电热转换。Preferably, the application includes applying the high temperature resistant electrothermal fiber to a high temperature environment with or generating 200-1200 degrees Celsius, and performing electrothermal conversion based on infrared radiation.
步骤1可以包括对纤维进行清洗的过程：将纤维依次置于环己烷、乙醇、去离子水中，对其超声清洗预定时间，比如10分钟，用氮气吹干，完成纤维的清洗。 Step 1 may include a process of cleaning the fibers: sequentially placing the fibers in cyclohexane, ethanol, and deionized water, ultrasonically cleaning them for a predetermined time, such as 10 minutes, and drying with nitrogen to complete the cleaning of the fibers.
该步骤中，所述纤维可以选自耐高温的石英纤维、玻璃纤维、石棉纤维、金属纤维、氮佬硼纤维、陶瓷纤维等能在300℃以上使用的纤维中的至少一种。即，所选纤维均为绝缘耐高温纤维材料。In this step, 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.
步骤2中的覆膜过程，优选通过覆金属工艺进行覆金属处理，金属 膜厚度不大于100μm。In the film coating process in step 2, 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.
该步骤中，所述涂覆金属选自铜、镍、铂等具有催化碳源裂解的金属中的至少一种。并且，所附膜层需要满足在300℃-1100℃的温度条件，和步骤4中反应过程中的压力条件下具有挥发效果。In this step, 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. In addition, 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.
该步骤中，所述覆金属工艺选自电镀、化学镀、溶胶-凝胶、磁控溅射、直接喷出金属涂层中的至少一种，优选为纳米金属粒子直接喷涂方式。In this step, 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.
步骤4中向反应腔内通入的可以为800-1000sccm Ar和800-1000sccm H2。生长时间可以控制在10-300分钟，优选40-300分钟，生长工艺设置为300℃-1100℃，从而在覆金属纤维表面形成厚度可控的微晶石墨层。In step 4, 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.
该步骤中，所述碳源选自气态(甲烷、乙烯、乙炔)、固态(聚苯胺、聚苯乙烯、等)、液态(甲苯、苯甲酸、氯苯、乙醇、乙腈等)碳源中的至少一种。In this step, 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.
步骤5具体包括：微晶石墨生长结束后，关闭碳源蒸气，将Ar和H2流量分布设置为100-300sccm/100-300sccm，开始降温过程，温度降至室温后关闭Ar/H2，将样品取出，完成整个制备过程。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.
上述制备过程中所涉及到的反应温度、各种气体流量、反应时间可以根据工艺需要进行调整。The reaction temperature, various gas flow rates, and reaction time involved in the above preparation process can be adjusted according to process requirements.
通过反复进行大量实验，并且对实验结果的进行错综复杂的对比分析，本申请的申请人发现了一种可以实现高红外发射率、低面电阻值、耐高温的电热纤维制备方法，本发明方法所制备的电热材料可以实现耐1200度高温、实现面电阻值低于100Ω/sq(实施例1中甚至低达10Ω/sq)、红外辐射率高于90％，基本达到95％(对应本发明的最佳实施方案)。Through repeated experiments and intricate comparative analysis of the experimental results, the applicant of the present application has discovered a method for preparing electrothermal fibers that can achieve high infrared emissivity, low surface resistance, and high temperature resistance. The prepared electric heating material can achieve high temperature resistance of 1200 degrees, realize the surface resistance value is lower than 100Ω/sq (even as low as 10Ω/sq in embodiment 1), and the infrared radiation rate is higher than 90%, basically reaching 95% (corresponding to the present invention Best Practice).
具体而言，申请人注意到，通过采用常温喷铜或镍、将铜或镍膜层厚度控制在25-60μm(优选40-60μm)，结合80-140分钟的生长时间，可以制备出面电阻值低于100/sq、红外辐射率95％、耐1200度高温的电热纤维。而采用其他方式所获得的电热纤维却无法在各方面都达到如此优异的性能。Specifically, the applicant noticed that by spraying copper or nickel at room temperature, controlling the thickness of the copper or nickel film at 25-60 μm (preferably 40-60 μm), combined with a growth time of 80-140 minutes, the surface resistance value can be prepared Electric heating fiber with lower than 100/sq, 95% infrared radiation rate and high temperature resistance of 1200 degrees. However, the electrothermal fiber obtained by other methods cannot achieve such excellent performance in all aspects.
本发明中的电热纤维由于采用中间纤维丝，外侧包覆微晶石墨的构 造，不仅可以增加电热纤维的韧性、透气性，还可以提高热辐射面积，进而进一步提高热转换效率，可以实现接近100％的电热转换效率。Due to the structure of the electric heating fiber in the present invention that 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.
本发明的方法成本低、成品率高并且制备出的电热纤维具有良好的疏水性、透气性等优异性能，具有巨大的社会价值和经济价值。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.
即便是本发明中的次优实施方案，也能够制备出耐500度以上高温、红外辐射率达到80％以上的电热纤维材料。Even in the sub-optimal embodiment of the present invention, it is possible to prepare an electrothermal fiber material that can withstand a high temperature of more than 500 degrees and an infrared radiation rate of more than 80%.
附图说明Description of the drawings
图1是化学气相沉积(CVD)***示意图。Figure 1 is a schematic diagram of a chemical vapor deposition (CVD) system.
图2是实施例1制备高温电热纤维布的实物图。2 is a physical diagram of the high-temperature electric heating fiber cloth prepared in Example 1.
图3是实施例1制备的电热纤维布的SEM图。3 is an SEM image of the electric heating fiber cloth prepared in Example 1.
图4是实施例1制备的电热纤维布电热图。4 is an electrothermal diagram of the electrothermal fiber cloth prepared in Example 1.
图5和图6是实施例1制备的电热纤维布的表面疏水特性展示图。5 and 6 are diagrams showing the hydrophobic properties of the surface of the electric heating fiber cloth prepared in Example 1.
图7是实施例1制备的电热纤维布的表面透气特性展示图。7 is a diagram showing the surface air permeability characteristics of the electric heating fiber cloth prepared in Example 1.
图8是实施例6制备的电热纤维布与金属丝电热膜电热性能曲线图。8 is a graph showing the electrothermal performance of the electrothermal fiber cloth and the metal wire electrothermal film prepared in Example 6.
具体实施方式detailed description
以下参照具体的实施例来说明本发明。本领域技术人员能够理解，这些实施例仅用于说明本发明，其不以任何方式限制本发明的范围。The present invention will be explained below with reference to specific embodiments. Those skilled in the art can understand that these embodiments are only used to illustrate the present invention, and they do not limit the scope of the present invention in any way.
下述实施例中的实验方法，如无特殊说明，均为常规方法。下述实施例中所用的生化试剂，载体耗材等，如无特殊说明，均为市售购买产品。The experimental methods in the following examples are conventional methods unless otherwise specified. The biochemical reagents and carrier consumables used in the following examples are all commercially available products unless otherwise specified.
实施例1Example 1
图1给出了常规化学气相沉积的设备，本发明的方法可以采用该设备来实现。如图所示，该设备主要包括左侧的气体供给部分，中间的高温管式炉以及右侧的冷却和气体排放装置。气体供给部分用于向高温管式炉中提供保护气体、还原气体以及碳源等，高温管式炉作为主要的反应设备，在其内进行微晶石墨生长，气体排放装置则用于反应剩余气体的处理。Figure 1 shows a conventional chemical vapor deposition equipment, and the method of the present invention can be implemented by using this equipment. As shown in the figure, 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.
产品制备时，采用超声清洗方式将石英纤维布清洗干净，利用常温喷铜(将质量分数20％的纳米铜粉(阿拉丁-C103844)超声分散于乙醇 溶液中，形成混合溶液，用普通油漆喷枪，即可直接喷出金属涂层的先进技术，此为现有技术这里不再详述)的方法在石英纤维表面包铜，形成铜的稀疏结构膜层(下同)，控制铜膜厚度为50μm(从而使得后续反应过程中金属无残留，申请人发现一旦纤维中有催化剂残留会出现纤维易老化断裂的情况)。When the product is prepared, the quartz fiber cloth is cleaned by ultrasonic cleaning, and copper is sprayed at room temperature (20% of the mass fraction of nano copper powder (Aladdin-C103844) is ultrasonically dispersed in the ethanol solution to form a mixed solution, and a common paint spray gun is used , You can directly spray the advanced technology of the metal coating, this is the prior art, 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 50μm (so that there is no metal residue in the subsequent reaction process, the applicant found that once there is catalyst residue in the fiber, the fiber will be easy to age and break).
接下来，将覆铜的石英纤维布放入直径为3英寸的1100℃的高温管式炉中，利用无油涡旋真空泵将高温管式炉内的反应腔中压强抽至100Pa以下，优选10Pa以下，通入Ar/H 2流量控制为1000/1000sccm，气流平稳后向反应腔中通入甲苯气体，将流量控制为1000sccm，甲苯蒸气进入反应腔后迅速裂解成活性碳物种，大量活性碳物种吸附到石英纤维表面，在表面迁移、碰撞，从而实现微晶石墨的成核和生长。碳材料生长过程设置为120分钟，生长结束后迅速关闭甲苯阀门，并将Ar/H 2设置为300/300sccm，开启降温过程。待反应腔内温度降至室温，关闭Ar/H 2，开仓取出样品。 Next, put 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. After the gas flow is stable, toluene gas is introduced into the reaction chamber, and the flow is controlled to 1000sccm. After the toluene vapor enters the reaction chamber, it is quickly cracked into activated carbon species, a large number of activated carbon species Adsorbed to the surface of quartz fiber, migrate and collide on the surface, so as to realize the nucleation and growth of microcrystalline graphite. 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. When the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
需要说明的是，碳源、保护气体、还原气体的流量可以根据需要适当调整，并不必须限制在实施例中的数值。比如，前期Ar/H 2流量可以控制为700-1300sccm；生长结束后Ar/H 2可以设置为200-500。 It should be noted that 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. For example, 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.
对所获得样品进行性能测试：采用液化气喷火枪对制备的电热纤维布进行耐热性实验，测试结果为：当温度大于1200℃时，持续高温5分钟后，纤维布才出现脆裂现象，但仍具有不燃的特性，说明本实施例的电热纤维材料能够耐1200℃高温；采用四探针测试仪对样品的面电阻值进行测试，测试结果为面电阻值为10Ω/sq；将4*4cm的纤维布两端贴附铜条作为导电电极，通过施加3V的直流/交流电，样品瞬间(小于1秒)可加热至100℃，呈现出较好速热特性、发热面均匀；采用JCY-2滴接触角测量仪测定纤维布接触角为100度，表现出疏水性的特性；将样品在100℃水蒸气环境中前后对比可知样品具有良好透气特性。采用TIR 100-2发射率快速测定仪，使被测样品表面接收100℃半球形黑体辐射出的红外辐射，然后再接收样品反射的红外辐射，测出红外辐射反射率并根据校准值得到样品(电热纤维布)的红外发射率，测量结果为，红外发射率0.95。采用德国布鲁克X射线能谱仪(QUANTAX EDS)***对样品微区成分元素种类分析，未检测出Cu元素残留。另外，通过对消耗电量和发热量进行分别测量，可以确定，其电热转换效率接近100％，可以达到 99％以上。Perform performance test on the obtained sample: use a liquefied gas torch to conduct a heat resistance test on the prepared electrothermal fiber cloth. The test result is: when the temperature is greater than 1200 ℃, the fiber cloth will be brittle after 5 minutes of high temperature. However, it still has non-combustibility characteristics, indicating that the electrothermal fiber material of this embodiment can withstand high temperatures of 1200°C; the surface resistance value of the sample is tested with a four-probe tester, and the test result is that the surface resistance value is 10Ω/sq; 4* Copper strips are attached to both ends of the 4cm fiber cloth as conductive electrodes. 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- The two-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 100 ℃ water vapor environment, it can be seen that the sample has good air permeability characteristics. The TIR 100-2 rapid emissivity tester is used to make the surface of the sample to be tested receive the infrared radiation radiated by a 100°C hemispherical black body, and then receive the infrared radiation reflected by the sample, measure the infrared radiation reflectivity and obtain the sample according to the calibration value ( The infrared emissivity of the heating fiber cloth), the measurement result is that the infrared emissivity is 0.95. Using 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. In addition, by separately measuring the power consumption and calorific value, it can be determined that the electrothermal conversion efficiency is close to 100% and can reach more than 99%.
另外，需要说明的是，本发明中所提到的耐火性能测试中的耐1200℃(下同)或其他温度的高温并非绝对的发生脆裂界限，只是当测试进行到该温度附近时再继续升温，会发现明显的脆裂现象，该温度的描述只是用于证明本发明产品的耐高温性能的大概程度。In addition, it should be noted that 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.
实施例2Example 2
准备石英纤维布，采用超声清洗方式将石英纤维布清洗干净，利用磁控溅射的方法在石英纤维表面包铜，控制铜膜厚度为50μm；将覆铜的石英纤维布放入1100℃的高温管式炉中，利用无油涡旋真空泵将反应腔内压强抽至10Pa以下，通入Ar/H 2流量控制为1000/1000sccm，气流平稳后打开甲苯气体阀门，通入甲苯气体，将流量控制为1000sccm，甲苯蒸气进入反应腔后迅速裂解成活性碳物种，大量活性碳物种吸附到石英纤维表面，在表面迁移、碰撞，从而实现微晶石墨的成核和生长。碳材料生长过程设置为120分钟，生长结束后迅速关闭甲苯阀门，并将Ar/H 2流量控制为300/300sccm，开启降温过程。待反应腔内温度降至室温，关闭Ar/H 2，开仓取出样品。 Prepare the quartz fiber cloth, clean the quartz fiber cloth by ultrasonic cleaning, use magnetron sputtering method to coat the surface of the quartz fiber with copper, and control the thickness of the copper film to 50μm; put the copper-clad quartz fiber cloth into a high temperature of 1100℃ In the tube furnace, use an oil-free scroll vacuum pump to pump the pressure in the reaction chamber below 10 Pa, and control the flow rate of Ar/H 2 to 1000/1000sccm. After the flow is stable, open the toluene gas valve and flow toluene gas to control the flow rate. At 1000 sccm, the toluene vapor quickly decomposes into activated carbon species after entering the reaction chamber, and a large amount of activated carbon species adsorbs to the surface of the quartz fiber, migrates and collides on the surface, thereby achieving 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.
对所获得样品进行性能测试：采用液化气喷火枪对制备的电热纤维布进行耐热性实验，测试结果为当温度大于800℃时，纤维布出现脆裂现象，说明本实施例的电热纤维材料能够耐800℃高温，较实施例1的实验结果有明显下降，但仍具有不燃的特性；采用四探针测试仪对样品的面电阻值进行测试，测试结果为面电阻值为10Ω/sq。采用TIR 100-2发射率快速测定仪，将被测样品表面接收100℃半球形黑体辐射出的红外辐射，样品反射的红外辐射被接收测出反射率并根据校准值得到红外辐射发射率，测量结果为，红外发射率0.86，较实施例1中的结构有所降低。采用德国布鲁克X射线能谱仪(QUANTAX EDS)***对样品微区成分元素种类分析，检测出少量Cu元素残留。申请人经过反复研究发现，通过磁控溅射获得的金属铜膜与纤维表面的结合力较大，在微晶石墨生长的过程中，不利于铜蒸气的挥发与扩散，因此，相同生长条件下，铜会出现残留的现象。金属铜在空气中高温的条件下易被氧化，从而引起样品耐热温度下降。同时，金属铜的红外发射率远远低于微晶石墨，因此样品2的红外发射率出现下降的现象。Perform a performance test on the obtained sample: use a liquefied gas torch to conduct a heat resistance test on the prepared electrothermal fiber cloth. The test result is that when the temperature is greater than 800°C, the fiber cloth appears brittle, indicating the electrothermal fiber material of this embodiment It can withstand a high temperature of 800°C, which is significantly lower than the experimental result of Example 1, but still has non-combustible characteristics; the surface resistance of the sample is tested by a four-probe tester, and the test result is that the surface resistance is 10Ω/sq. Using the TIR 100-2 rapid emissivity tester, 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 according to the calibration value. As a result, the infrared emissivity was 0.86, which was 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. After repeated studies, the applicant found that the metal copper film obtained by magnetron sputtering has a greater bonding force with the fiber surface. During the growth of microcrystalline graphite, it is not conducive to the volatilization and diffusion of copper vapor. Therefore, under the same growth conditions , Copper will appear residual phenomenon. Metal copper is easily oxidized under high temperature conditions in the air, which causes the heat resistance temperature of the sample to drop. At the same time, the infrared emissivity of metallic copper is much lower than that of microcrystalline graphite, so the infrared emissivity of sample 2 appears to decrease.
实施例3Example 3
准备石英纤维布，采用超声清洗方式将石英纤维布清洗干净，利用常温喷镍的方法在石英纤维表面包镍，控制镍膜厚度为30μm；将覆镍的石英纤维放入400℃的高温管式炉中，利用无油涡旋真空泵将反应腔内压强抽至10Pa以下，在反应腔中通入Ar/H 2流量控制为1000/1000sccm，Ar/H 2气流平稳后打开乙烯气体阀门，通入乙烯气体将流量控制为1000sccm，乙烯气进入反应腔后迅速裂解成活性碳材料，大量活性碳材料吸附到石英纤维表面，在表面迁移、碰撞，从而实现微晶石墨的成核和生长。碳材料生长过程设置为120分钟，生长结束后迅速关闭乙烯阀门，并将Ar/H 2流量控制为300/300sccm，开启降温过程。待反应腔内温度降至室温，关闭Ar/H 2，开仓取出样品。 Prepare the quartz fiber cloth, clean the quartz fiber cloth by ultrasonic cleaning method, use the method of spraying nickel at room temperature to coat the surface of the quartz fiber with nickel, and control the thickness of the nickel film to 30μm; put the nickel-coated quartz fiber into the high temperature tube at 400℃ In the furnace, use an oil-free vortex vacuum pump to pump the pressure in the reaction chamber below 10 Pa, and control the flow of Ar/H 2 into the reaction chamber to 1000/1000 sccm. After the Ar/H 2 flow is stable, open the ethylene gas valve and let it in The flow rate of ethylene gas is controlled to 1000 sccm. After entering the reaction chamber, the ethylene gas is quickly cracked into activated carbon material. 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.
对所获得样品进行性能测试：采用液化气喷火枪对制备的电热纤维进行耐热性实验，测试结果为当温度大于1200℃时，纤维开始出现脆裂现象，具有不燃的特性；采用四探针测试仪对样品的面电阻值进行测试，测试结果为面电阻值为100Ω/sq。采用TIR 100-2发射率快速测定仪，使被测样品表面接收100℃半球形黑体辐射出的红外辐射，然后再接收样品反射的红外辐射，测出红外辐射反射率并根据校准值得到红外辐射发射率，测量结果为，红外发射率0.96。采用德国布鲁克X射线能谱仪(QUANTAX EDS)***对样品微区成分元素种类分析，未检测出镍元素残留。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℃, the fiber begins to crack and has non-combustible characteristics; four probes are used The tester tests the surface resistance value of the sample, and the test result is that the surface resistance value is 100Ω/sq. Using the TIR 100-2 rapid emissivity tester, the surface of the sample to be tested receives the infrared radiation radiated by a 100℃ hemispherical black body, and then receives the infrared radiation reflected by the sample, measures the infrared radiation reflectivity and obtains the infrared radiation according to the calibration value Emissivity, the measurement result is that the infrared emissivity is 0.96. Using 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.
本实施例所制备的样品较实施例1大大降低了生长温度，经分析可知，在T＝773～1573K温度范围内，碳在镍中固溶度较高，碳源在高温条件下于镍金属表面催化裂解后形成的碳原子或碳自由基会进入到镍金属基底体相里，降温时再从镍金属体相析出到表面形成较厚的微晶石墨层。The sample prepared in this example has a much lower growth temperature than that in Example 1. The analysis shows that in the temperature range of T=773～1573K, the solid solubility of carbon in nickel is higher, and the carbon source is lower than nickel metal under high temperature conditions. The carbon atoms or carbon radicals formed after catalytic cracking on the surface 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.
实施例4Example 4
准备石英纤维布，采用超声清洗方式将石英纤维布清洗干净，利用常温喷镍的方法在石英纤维表面包镍，控制镍膜厚度为30μm；将覆镍的石英纤维放入300℃的高温管式炉中，利用无油涡旋真空泵将反应腔内压强抽至10Pa以下，在反应腔中通入Ar/H 2流量控制为1000/1000sccm，气流平稳后打开甲苯气体阀门，通入甲苯气体将流量控制为1000sccm，甲苯气进入反应腔后迅速裂解成活性碳物种，大量活性碳物种吸附到石英纤维表面，在表面迁移、碰撞，从而实现微晶石墨的成核和生长。碳材料生长过程设置为120分钟，生长结束后迅速关闭甲苯阀门，并将Ar/H 2 流量控制为300/300sccm，开启降温过程。待反应腔内温度降至室温，关闭Ar/H 2，开仓取出样品。 Prepare the quartz fiber cloth, clean the quartz fiber cloth by ultrasonic cleaning method, use the method of spraying nickel at room temperature to coat the surface of the quartz fiber with nickel, and control the thickness of the nickel film to 30μm; put the nickel-coated quartz fiber into a high temperature tube at 300℃ In the furnace, use an oil-free vortex vacuum pump to pump the pressure in the reaction chamber below 10 Pa, and control the flow of Ar/H 2 into the reaction chamber to be 1000/1000 sccm. After the air flow is stable, open the toluene gas valve and pass in toluene gas to reduce the flow Controlled to 1000sccm, the toluene gas quickly decomposes into activated carbon species after entering the reaction chamber, and a large number of activated carbon species are adsorbed on the surface of the quartz fiber, migrate and collide 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.
对所获得样品进行性能测试：采用液化气喷火枪对制备的电热纤维进行耐热性实验，测试结果为当温度大于1200℃时，纤维开始出现脆裂现象，具有不燃的特性，而在1200℃以下时，持续高温5分钟基本不发生脆裂；采用四探针测试仪对样品的面电阻值进行测试，测试结果为面电阻值为150Ω/sq。采用TIR 100-2发射率快速测定仪，使被测样品表面接收100℃半球形黑体辐射出的红外辐射，然后再接收样品反射的红外辐射，测出红外辐射反射率并根据校准值得到红外辐射发射率，测量结果为，红外发射率0.96。采用德国布鲁克X射线能谱仪(QUANTAX EDS)***对样品微区成分元素种类分析，未检测出镍元素残留。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 1200 ℃, the fiber starts to appear brittle and has non-combustible characteristics. Under the following conditions, there is basically no embrittlement after 5 minutes of continuous high temperature; the surface resistance value of the sample is tested with a four-probe tester, and the test result is that the surface resistance value is 150Ω/sq. Using the TIR 100-2 rapid emissivity tester, the surface of the sample to be tested receives the infrared radiation radiated by a 100℃ hemispherical black body, and then receives the infrared radiation reflected by the sample, measures the infrared radiation reflectivity and obtains the infrared radiation according to the calibration value Emissivity, the measurement result is that the infrared emissivity is 0.96. Using 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.
本实施例所制备的样品较实施例3的样品，生长温度降至300°，经分析可知，通过控制甲苯在镍金属催化的条件下可是实现低温裂解，并存在大量的苯环自由基，可实现六角型呈蜂巢碳晶格快速堆叠。Compared with the sample in Example 3, the growth temperature of the sample prepared in this example is lowered 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 free radicals. Realize the rapid stacking of hexagonal honeycomb carbon lattice.
实施例5Example 5
准备石英纤维布，采用超声清洗方式将石英纤维布清洗干净，利用常温喷镍的方法在石英纤维表面包镍，控制镍膜厚度为10μm；将覆镍的石英纤维放入400℃的高温管式炉中，利用无油涡旋真空泵将反应腔内压强抽至10Pa以下，通入Ar/H 2流量控制为1000/1000sccm，气流平稳后打开甲苯气体阀门，将流量控制为1000sccm，甲苯气进入反应腔后迅速裂解成活性碳物种，大量活性碳物种吸附到石英纤维表面，在表面迁移、碰撞，从而实现微晶石墨的成核和生长。碳材料生长过程设置为20分钟，生长结束后迅速关闭甲苯阀门，并将Ar/H 2流量控制为300/300sccm，开启降温过程。待反应腔内温度降至室温，关闭Ar/H 2，开仓取出样品。 Prepare the quartz fiber cloth, clean the quartz fiber cloth by ultrasonic cleaning method, use the method of spraying nickel at room temperature to coat the surface of the quartz fiber with nickel, and control the thickness of the nickel film to 10μm; put the nickel-coated quartz fiber into the high temperature tube at 400℃ In the furnace, use an oil-free scroll vacuum pump to pump the pressure in the reaction chamber below 10Pa, and control the flow of Ar/H 2 to 1000/1000sccm. After the airflow is stable, open the toluene gas valve and control the flow to 1000sccm. The toluene gas enters the reaction. After the cavity, it quickly decomposes into activated carbon species, and a large number of activated carbon species adsorb to the surface of the quartz fiber, migrate and collide on the surface, so as to realize 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. When the temperature in the reaction chamber drops to room temperature, turn off Ar/H 2 , open the chamber and take out the sample.
对所获得样品进行性能测试：采用液化气喷火枪对制备的电热纤维进行耐热性实验，测试结果为当温度大于1200℃时，纤维开始出现脆裂现象，具有不燃的特性；采用四探针测试仪对样品的面电阻值进行测试，测试结果为面电阻值为1800Ω/sq。采用TIR 100-2发射率快速测定仪，使被测样品表面接收100℃半球形黑体辐射出的红外辐射，，然后再接收样品反射的红外辐射，测出反射率并根据校准值得到样品的红外发射率，测量结果为，红外发射率0.96。采用德国布鲁克X射线能谱仪(QUANTAX  EDS)***对样品微区成分元素种类分析，未检测出镍元素残留。本实施例的样品较实施例4样品，电阻值增大，经分析可知，通过控制镍金属催化剂的含量及生长时间，可以控制纤维表面微晶石墨层的厚度，厚度越大，电阻值越低。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℃, the fiber begins to crack and has non-combustible characteristics; four probes are used The tester tests the surface resistance of the sample, and the test result is that the surface resistance is 1800Ω/sq. Using the TIR 100-2 rapid emissivity tester, 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 reflectivity and obtains the infrared radiation of the sample according to the calibration value Emissivity, the measurement result is that the infrared emissivity is 0.96. The German Bruker X-ray energy spectrometer (QUANTAX EDS) system was used to analyze the types of elements in the sample micro-area, and no nickel residue was detected. Compared with the sample of Example 4, the resistance value of the sample of this example is higher. The analysis shows that by controlling the content of the nickel metal catalyst and the growth time, the thickness of the microcrystalline graphite layer on the fiber surface can be controlled. The greater the thickness, the lower the resistance value. .
实施例6Example 6
准备玻璃纤维布，采用超声清洗方式将玻璃纤维布清洗干净，利用常温喷镍方法在玻璃纤维表面包镍，控制镍膜厚度为30μm；将覆镍的玻璃纤维布放入500℃的高温管式炉中，利用无油涡旋真空泵将反应腔内压强抽至10Pa以下，通入Ar/H 2流量控制为1000/1000sccm，气流平稳后打开甲苯气体阀门，将流量控制为1000sccm，甲苯蒸气进入反应腔后迅速裂解成活性碳物种，大量活性碳物种吸附到玻璃纤维表面，在表面迁移、碰撞，从而实现微晶石墨的成核和生长。碳材料生长过程设置为120分钟，生长结束后迅速关闭甲苯阀门，并将Ar/H 2流量控制为300/300sccm，开启降温过程。待反应腔内温度降至室温，关闭Ar/H 2，开仓取出样品。 Prepare glass fiber cloth, use ultrasonic cleaning method to clean the glass fiber cloth, use the method of spraying nickel at room temperature to coat the surface of the glass fiber with nickel, and control the thickness of the nickel film to 30μm; put the nickel-coated glass fiber cloth into a high temperature tube at 500℃ In the furnace, use an oil-free scroll vacuum pump to pump the pressure in the reaction chamber below 10Pa, and control the flow of Ar/H 2 to 1000/1000sccm. After the airflow is stable, open the toluene gas valve and control the flow to 1000sccm. The toluene vapor enters the reaction. After the cavity is quickly decomposed into activated carbon species, a large number of activated carbon species are adsorbed on the surface of the glass fiber, migrate and collide 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 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.
对所获得样品进行性能测试：采用液化气喷火枪对制备的电热纤维布进行耐热性实验，测试结果为当温度大于700℃时，纤维布开始出现脆裂现象，但仍具有不燃的特性；采用四探针测试仪对样品进行测试，测试结果为面电阻值为230Ω/sq；采用德国布鲁克X射线能谱仪(QUANTAX EDS)***对样品微区成分元素种类分析，未检测出镍元素残留。分别取2*2cm的金属丝电热膜与微晶石墨纤维布进行电热性能测试。测试结果表明，微晶石墨烯纤维布升温速度快，且热稳定性好。通过计算可知，微晶石墨纤维布的热电转化率为91.4％，金属丝电热膜的热电转化率为82.1％。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 ℃, the fiber cloth begins to crack, but it still has the characteristics of non-combustibility; A four-probe tester was used to test the sample, and the test result was that the surface resistance value was 230Ω/sq; the German Bruker X-ray energy spectrometer (QUANTAX EDS) system was used to analyze the types of elements in the sample micro-area, and no nickel residue was detected. . Take 2*2cm metal wire electric heating film and microcrystalline graphite fiber cloth to test the electric heating performance. The test results show that the microcrystalline graphene fiber cloth has a fast heating speed and good thermal stability. The calculation shows that the 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%.
实施例7Example 7
准备石英纤维布，采用超声清洗方式将石英纤维布清洗干净，利用常温喷铜的方法在石英纤维表面包铜，控制铜膜厚度为1μm；将覆镍的石英纤维放入1100℃的高温管式炉中，利用无油涡旋真空泵将反应腔内压强抽至10Pa以下，通入Ar/H 2流量控制为1000/1000sccm，气流平稳后打开乙烯气体阀门，将流量控制为1000sccm，乙烯气进入反应腔后迅 速裂解成活性碳物种，大量活性碳物种吸附到石英纤维表面，在表面迁移、碰撞，从而实现微晶石墨的成核和生长。碳材料生长过程设置为120分钟，生长结束后迅速关闭乙烯阀门，并将Ar/H 2流量控制为300/300sccm，开启降温过程。待反应腔内温度降至室温，关闭Ar/H 2，开仓取出样品。 Prepare the quartz fiber cloth, clean the quartz fiber cloth by ultrasonic cleaning, use the method of spraying copper at room temperature to coat the surface of the quartz fiber, and control the thickness of the copper film to 1μm; put the nickel-coated quartz fiber into the high temperature tube at 1100℃ In the furnace, use an oil-free scroll vacuum pump to pump the pressure in the reaction chamber below 10Pa, and control the flow of Ar/H 2 to 1000/1000sccm. After the airflow is stable, open the ethylene valve to control the flow to 1000sccm, and the ethylene gas enters the reaction. After the cavity, it quickly decomposes into activated carbon species, and a large number of activated carbon species adsorb to the surface of the quartz fiber, migrate and collide 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.
对所获得样品进行性能测试：采用液化气喷火枪对制备的电热纤维进行耐热性实验，测试结果为当温度大于1200℃时，纤维开始出现脆裂现象，具有不燃的特性；采用四探针测试仪对样品的的面电阻值进行测试，测试结果为面电阻值大于10MΩ/sq。采用TIR 100-2发射率快速测定仪，将被测样品表面接收100℃半球形黑体辐射出的红外辐射，样品7反射的红外辐射被接收测出反射率并根据校准值得到红外辐射发射率，测量结果为，红外发射率0.48，红外发射率大幅度降低。采用德国布鲁克X射线能谱仪(QUANTAX EDS)***对样品微区成分元素种类分析，未检测出铜元素残留。经分析可知，由于铜膜厚度太薄，铜在高温条件下迅速挥发，并通过抽真空将铜蒸汽迅速抽离反应腔体，铜蒸汽浓度过低，未启到有效的催化效果，导致碳物种颗粒以无定型碳的形式沉积在纤维表面，因此，样品7的电阻值急剧增大，红外发射率大幅降低。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℃, the fiber begins to crack and has non-combustible characteristics; four probes are used The tester tests the surface resistance value of the sample, and the test result is that the surface resistance value is greater than 10MΩ/sq. Using the TIR 100-2 rapid emissivity tester, the surface of the tested sample receives the infrared radiation radiated by a 100°C hemispherical black body, and the infrared radiation reflected by the sample 7 is received to measure the reflectivity and obtain the infrared radiation emissivity according to the calibration value. The measurement result is that the infrared emissivity is 0.48, and the infrared emissivity is greatly reduced. Using the German Bruker X-ray energy spectrometer (QUANTAX EDS) system to analyze the types of elements in the sample micro-area, 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 the copper vapor is too low to achieve an effective catalytic effect, resulting in carbon species 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.
实施例8Example 8
准备石英纤维布，采用超声清洗方式将石英纤维布清洗干净，利用常温喷铜的方法在石英纤维表面包铜，控制铜膜厚度为200μm；将覆铜的石英纤维放入1100℃的高温管式炉中，利用无油涡旋真空泵将反应腔内压强抽至10Pa以下，通入Ar/H 2流量控制为1000/1000sccm，气流平稳后打开乙烯气体阀门，将流量控制为1000sccm，乙烯气进入反应腔后迅速裂解成活性碳物种，大量活性碳物种吸附到石英纤维表面，在表面迁移、碰撞，从而实现微晶石墨的成核和生长。碳材料生长过程设置为120分钟，生长结束后迅速关闭乙烯阀门，并将Ar/H 2流量控制为300/300sccm，开启降温过程。待反应腔内温度降至室温，关闭Ar/H 2，开仓取出样品。 Prepare the quartz fiber cloth, clean the quartz fiber cloth by ultrasonic cleaning, use the method of spraying copper at room temperature to coat the surface of the quartz fiber, and control the thickness of the copper film to 200μm; put the copper-clad quartz fiber into the high temperature tube at 1100℃ In the furnace, use an oil-free scroll vacuum pump to pump the pressure in the reaction chamber below 10Pa, and control the flow of Ar/H 2 to 1000/1000sccm. After the airflow is stable, open the ethylene valve to control the flow to 1000sccm, and the ethylene gas enters the reaction. After the cavity, it quickly decomposes into activated carbon species, and a large number of activated carbon species adsorb to the surface of the quartz fiber, migrate and collide 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.
对所获得样品进行性能测试：采用液化气喷火枪对制备的电热纤维进行耐热性实验，测试结果为当温度大于600℃时，纤维开始出现脆裂现象，具有不燃的特性；采用四探针测试仪对样品的面电阻值进行测试，测试结果为面电阻值8Ω/sq。采用TIR 100-2发射率快速测定仪，将被测 样品表面接收100℃半球形黑体辐射出的红外辐射，样品8反射的红外辐射被接收测出反射率并根据校准值得到样品的红外辐射发射率，测量结果为，红外发射率0.53。采用德国布鲁克X射线能谱仪(QUANTAX EDS)***对样品微区成分元素种类分析，检测出大量铜元素残留。经分析可知，由于铜膜厚度太厚，铜在高温生长的过程存在大量的残留，形成了纤维/铜/微晶石墨的复合材料。因此降低材料的电阻值及红外发热率。同时，铜膜厚度的增加也增加了材料的生产成本。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 ℃, the fiber begins to crack and has non-combustible characteristics; four probes are used The tester tests the surface resistance of the sample, and the test result is 8Ω/sq. Using the TIR 100-2 rapid emissivity tester, 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 8 is received to measure the reflectivity and obtain the infrared radiation emission 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.
需要说明的是，虽然上述实施例中均是以电热纤维布的形势进行的描述，但是本发明不仅限于电热纤维布的制备，电热纤维丝、电热纤维网或者电热纤维所能构成的其他构造都可以通过本发明的方法实现。It should be noted that although the foregoing embodiments are all described in the form of electric heating fiber cloth, the present invention is not limited to the preparation of electric heating fiber cloth, and other structures that can be formed by electric heating fiber filaments, electric heating fiber nets or electric heating fibers are all This can be achieved by the method of the present invention.
以上对本发明具体实施方式的描述并不限制本发明，本领域技术人员可以根据本发明作出各种改变或变形，只要不脱离本发明的精神，任何基于本发明技术方案的等效变换、简单替换等显而易见的改变，均落在本发明保护范围之内。The above description of the specific embodiments of the present invention does not limit the present invention. Those skilled in the art can make various changes or modifications according to the present invention, as long as they do not depart from the spirit of the present invention, any equivalent changes or simple replacements based on the technical solutions of the present invention Such obvious changes fall within the protection scope of the present invention.

Claims (10)

  1. 一种耐高温电热纤维的制备方法，其特征在于，所述方法包括下述步骤：A method for preparing high temperature resistant electric heating fibers, characterized in that the method includes the following steps:
    步骤1：准备绝缘的纤维材料；Step 1: Prepare insulating fiber material;
    步骤2：对所述纤维材料进行表面覆膜处理，所覆的膜层包含碳源裂解催化材料；Step 2: Perform surface coating treatment on the fiber material, and the coating layer contains a carbon source cracking catalytic material;
    步骤3：将覆膜后的所述纤维材料置于真空反应腔中；Step 3: Place the coated fiber material in a vacuum reaction chamber;
    步骤4：向所述真空反应腔中通入保护气体和还原性气体，然后通入碳源，进行微晶石墨生长；Step 4: Pass protective gas and reducing gas into the vacuum reaction chamber, and then pass in a carbon source to grow microcrystalline graphite;
    步骤5：在保护气体和还原性气体氛围下，对所述纤维材料进行降温，获得耐高温电热纤维。Step 5: cooling the fiber material under a protective gas and reducing gas atmosphere to obtain a high-temperature resistant electric heating fiber.
  2. 根据权利要求1所述的耐高温电热纤维的制备方法，其特征在于，所述纤维材料为耐高温纤维，所述纤维材料选自单根纤维、单束纤维以及纤维布中的至少一种。The method for preparing high temperature resistant electric heating fibers according to claim 1, wherein the fiber material is a high temperature resistant fiber, and the fiber material is selected from at least one of a single fiber, a single fiber and a fiber cloth.
  3. 根据权利要求1所述的耐高温电热纤维的制备方法，其特征在于，所述碳源裂解催化材料为金属碳源裂解催化材料。The method for preparing high-temperature resistant electric heating fibers according to claim 1, wherein the carbon source cracking catalytic material is a metal carbon source cracking catalytic material.
  4. 根据权利要求1所述的耐高温电热纤维的制备方法，其特征在于，所覆膜层的厚度为10-100μm。The method for preparing high temperature resistant electric heating fiber according to claim 1, wherein the thickness of the film layer is 10-100 μm.
  5. 根据权利要求4所述的耐高温电热纤维的制备方法，其特征在于，所覆膜层的厚度小于60μm。The method for preparing high temperature resistant electric heating fiber according to claim 4, wherein the thickness of the film layer is less than 60 μm.
  6. 根据权利要求1所述的耐高温电热纤维的制备方法，其特征在于，所述保护气体包括惰性气体，所述还原性气体包括H 2，所述步骤4还包括待保护气体和还原性气体的气流稳定后，再通入碳源。 The method for preparing high-temperature resistant electric heating fibers according to claim 1, wherein the protective gas includes an inert gas, the reducing gas includes H 2 , and the step 4 also includes a combination of the protective gas and the reducing gas. After the airflow stabilizes, the carbon source is introduced.
  7. 根据权利要求1所述的耐高温电热纤维的制备方法，其特征在于，所述碳源裂解催化材料为在反应温度和低压条件下的挥发性材料。The method for preparing high temperature resistant electric heating fiber according to claim 1, wherein the carbon source cracking catalytic material is a volatile material under reaction temperature and low pressure conditions.
  8. 根据权利要求1所述的耐高温电热纤维的制备方法，其特征在于，所述碳源选自甲烷、乙烯、乙炔、聚苯胺、聚苯乙烯、甲苯、苯甲酸、氯苯、乙醇以及乙腈中的至少一种。The method for preparing high temperature resistant electric heating fiber according to claim 1, wherein the carbon source is selected from methane, ethylene, acetylene, polyaniline, polystyrene, toluene, benzoic acid, chlorobenzene, ethanol, and acetonitrile At least one of.
  9. 一种权利要求1-8中任意一项所述方法制备的耐高温电热纤维的应用，所述应用包括在所述耐高温电热纤维两端施加电压，以进行电热转换，优选地，所述应用包括将所述耐高温电热纤维应用于具有或产生200-1200摄氏度的高温环境中，以红外辐射方式进行电热转换。An application of the high-temperature resistant electric heating fiber prepared by the method of any one of claims 1-8, the application comprising applying a voltage to both ends of the high-temperature resistant electric heating fiber to perform electrothermal conversion. Preferably, the application It includes applying the high temperature resistant electric heating fiber to a high temperature environment with or producing 200-1200 degrees Celsius, and performing electric heating conversion by infrared radiation.
  10. 一种权利要求1-8中任意一项所述方法制备的耐高温电热纤维。A high-temperature resistant electric heating fiber prepared by the method of any one of claims 1-8.
PCT/CN2019/091444 2019-04-04 2019-06-16 Preparation and use of high temperature resistant electrothermal fiber WO2020199353A1 (en)

Applications Claiming Priority (2)

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