CN110022623B - Preparation and application of high-temperature-resistant electric heating fiber - Google Patents

Preparation and application of high-temperature-resistant electric heating fiber Download PDF

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CN110022623B
CN110022623B CN201910272749.4A CN201910272749A CN110022623B CN 110022623 B CN110022623 B CN 110022623B CN 201910272749 A CN201910272749 A CN 201910272749A CN 110022623 B CN110022623 B CN 110022623B
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fiber
temperature
gas
electrothermal
electric heating
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CN110022623A (en
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李辰宇
汪威
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Carbon Weng (beijing) Technology Co Ltd
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Carbon Weng (beijing) Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/26Deposition of carbon only
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/10Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12Heater 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
    • H05B3/14Heater 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
    • H05B3/145Carbon only, e.g. carbon black, graphite
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/40Heating elements having the shape of rods or tubes
    • H05B3/54Heating elements having the shape of rods or tubes flexible

Abstract

The invention provides a preparation method and application of high-temperature-resistant electrothermal fibers, wherein the method comprises the following steps: step 1: preparing a cleaned fibrous material; step 2: carrying out surface coating treatment on the fiber material, wherein the coated film layer contains a carbon source cracking catalytic material; and step 3: placing the fiber material coated with the film in a vacuum reaction cavity; and 4, step 4: introducing inert gas and H into the vacuum reaction chamber2After the airflow is stable, introducing a carbon source to grow the microcrystalline graphite; and 5: in the presence of inert gas and H2And cooling the fiber material in the atmosphere to obtain the high-temperature-resistant electric heating fiber.

Description

Preparation and application of high-temperature-resistant electric heating fiber
Technical Field
The invention belongs to the field of materials, and particularly relates to a method for preparing high-temperature-resistant electric heating fibers by using a Chemical Vapor Deposition (CVD) method, which expands the application of the fibers in the field of electric heating components.
Background
With the rapid development of the industries such as aerospace, electronics and electricians, metallurgy and chemical engineering, traffic, automobiles, military industry and the like, the requirements on hot-working forming and heat treatment conditions of materials are more and more strict. Therefore, research and development of heating methods and novel heating materials have become hot research points in the fields of material science and energy development.
Electrocaloric materials are used to manufacture heating elements in various resistance heating devices. At present, the electric heating is widely applied because of the advantages of easy control and adjustment, no environmental pollution, contribution to improving the product quality and the like. The resistance heating mode using resistance heating element as electrothermal conversion is the most simple and convenient and widely applied. Common electrocaloric materials include both metallic and non-metallic electrocaloric materials. The main disadvantages of metallic electrocaloric materials are their high price and their harsh conditions of use, where refractory metallic electrocaloric materials must be used in vacuum or protective atmosphere. Metal electrothermal materials are usually processed into a wire spiral or wave structure, and easily generate an inductive reactance effect when electrified to cause energy loss. Compared with metal electric heating materials, the nonmetal electric heating materials have the advantages of high temperature resistance, corrosion resistance, oxidation resistance, high electric heating conversion efficiency and the like, and the nonmetal electric heating materials gradually replace the metal electric heating materials in both high-temperature heating fields and medium-low temperature heating fields. However, the nonmetal electric heating element is processed into a rod shape, a strip shape, a plate shape, a U shape and the like through a biscuit firing process and a sintering process, and the problems of large dispersion of element resistance, poor mechanical property and the like cannot be solved. Therefore, the research and development of the novel high-performance electric heating material not only has important scientific research significance, but also has important practical application value.
Disclosure of Invention
The invention aims to provide a preparation method of a high-temperature-resistant electric heating fiber material. Microcrystalline graphite is a mixture of carbon atoms in sp2The hybrid tracks form a hexagonal honeycomb lattice which is randomly distributed on the substrate to form the carbon nano material with disordered superstructure. The far infrared emissivity of the electrothermal fiber prepared by the invention is as high as 0.95, the heat conversion rate can be effectively improved, and the electric energy consumption is reduced; the high-temperature-resistant flexible heat-insulating material has the outstanding advantages of high temperature resistance, flexibility, easiness in configuration, adjustable resistivity and the like, and has the advantages of small thermal inertia, closer contact with a heated body, small heat conduction loss and the like. Can extend the application range of the traditional electric heating material, such as household appliances, electronics, medical treatment, traffic, space navigation and other fields.
Specifically, in a first aspect, the present invention provides a method for preparing a high temperature resistant electrothermal fiber, which is characterized by comprising the following steps:
step 1: preparing a cleaned fibrous material;
step 2: carrying out surface coating treatment on the fiber material, wherein the coated film layer contains a carbon source cracking catalytic material;
and step 3: placing the fiber material coated with the film in a vacuum reaction cavity;
and 4, step 4: introducing protective gas and reducing gas into the vacuum reaction cavity, and then introducing a carbon source to perform microcrystalline graphite growth;
and 5: and cooling the fiber material in the atmosphere of protective gas and reducing gas to obtain the high-temperature-resistant electric heating fiber.
Preferably, the fiber material is selected from at least one of single fiber, single bundle fiber and fiber cloth.
Preferably, the carbon source cracking catalytic material is a metal carbon source cracking catalytic material.
Preferably, the thickness of the applied layer is 10 to 100. mu.m, more preferably 40 to 60 μm.
Preferably, the protective gas comprises an inert gas, the reducing gas comprises H2, and the step 4 further comprises introducing a carbon source after the flow of the protective gas and the reducing gas is stabilized.
Preferably, the carbon source cracking catalytic material is a volatile material under the conditions of reaction temperature and low pressure.
In another aspect, the invention provides a high-temperature resistant electrothermal fiber, which is characterized by comprising a fiber layer and a microcrystalline graphite layer coated outside the fiber layer.
Preferably, the microcrystalline graphite layer is coated outside the fiber layer by the following method:
step 1: preparing a cleaned fibrous material;
step 2: carrying out surface coating treatment on the fiber material, wherein the coated film layer contains a carbon source cracking catalytic material;
and step 3: placing the fiber material coated with the film in a vacuum reaction cavity;
and 4, step 4: introducing protective gas and reducing gas into the vacuum reaction cavity, and then introducing a carbon source to perform microcrystalline graphite growth;
and 5: and cooling the fiber material in the atmosphere of protective gas and reducing gas to obtain the high-temperature-resistant electric heating fiber.
In another aspect, the invention provides a use of the high temperature resistant electrothermal fiber, the use comprising applying a voltage across the high temperature resistant electrothermal fiber to perform electrothermal conversion.
Preferably, the application comprises applying the high-temperature resistant electrothermal fiber to a high-temperature environment with or generating 200-1200 ℃ for electrothermal conversion in an infrared radiation mode.
Step 1 may include a process of washing the fiber: and (3) putting the fibers in cyclohexane, ethanol and deionized water in sequence, ultrasonically cleaning for 10 minutes, and blow-drying by using nitrogen to finish the cleaning of the fibers.
In the step, the fiber can be at least one of high-temperature resistant quartz fiber, glass fiber, asbestos fiber, metal fiber, nitrogen Laolab fiber, ceramic fiber and the like which can be used at the temperature of more than 300 ℃. Namely, the selected fibers are all insulating high-temperature resistant fiber materials.
In the film coating process in the step 2, preferably, the metal coating process is performed through a metal coating process, and the thickness of the metal film is not more than 100 μm.
In this step, the coating metal is at least one selected from metals having catalytic carbon source cracking, such as copper, nickel, and platinum. And, the attached film layer needs to satisfy the volatilization effect under the temperature condition of 300 ℃ to 1100 ℃ and the pressure condition during the reaction in step 4.
In the step, the metal coating process is at least one selected from electroplating, chemical plating, sol-gel, magnetron sputtering and direct spraying of a metal coating.
In the step 4, the flow rate of Ar in the reaction chamber can be 800-1000sccm and 800-1000sccm H2. The growth time can be controlled within 10-300 minutes, preferably 40-300 minutes, and the growth process is set to 300-1100 ℃, so that a microcrystalline graphite layer with controllable thickness is formed on the surface of the metal-coated fiber.
In this step, the carbon source is selected from at least one of gaseous (methane, ethylene, acetylene), solid (polyaniline, polystyrene, etc.), liquid (toluene, benzoic acid, chlorobenzene, ethanol, acetonitrile, etc.) carbon sources.
The step 5 specifically comprises the following steps: and after the growth of the microcrystalline graphite is finished, closing carbon source steam, setting the flow distribution of Ar and H2 as 300sccm (100) and 300sccm, starting a cooling process, closing Ar/H2 after the temperature is reduced to room temperature, taking out a sample, and finishing the whole preparation process.
The reaction temperature, various gas flow rates and reaction time involved in the preparation process can be adjusted according to the process requirements.
Through repeated experiments and complicated comparative analysis of experimental results, the applicant of the present application finds a preparation method of an electrothermal fiber capable of realizing high far infrared emissivity, low sheet resistance value and high temperature resistance, and a preparation method capable of realizing high temperature resistance of 1200 ℃, sheet resistance value lower than 100 Ω/sq (even as low as 10 Ω/sq in example 1), infrared emissivity higher than 90% and basically higher than 95% (corresponding to the best embodiment of the present invention).
Specifically, the applicant notices that the electrothermal fiber with the surface resistance value lower than 100/sq, the infrared radiance of 95 percent and the high temperature resistance of 1200 ℃ can be prepared by spraying copper or nickel at normal temperature, controlling the thickness of a copper or nickel film layer to be 25-60 mu m (preferably 40-60 mu m) and combining the growth time of 80-140 minutes. The electrothermal fiber obtained by other methods cannot achieve such excellent performance in all aspects.
The electric heating fiber adopts the structure that the middle fiber wire is coated with the microcrystalline graphite, so that compared with a carbon fiber electric heating material, the electric heating fiber has the advantages that the toughness and the air permeability of the electric heating fiber are improved, the heat radiation area is increased, the heat conversion efficiency is further improved, and the electric heating conversion efficiency close to 100 percent can be realized.
The method has low cost and high yield, and the prepared electrothermal fiber has good performances of hydrophobicity, air permeability and the like, and has great social value and economic value.
Even if the method is implemented less optimally, the method can prepare the electrothermal fiber material which can resist the high temperature of more than 500 ℃ and has the infrared radiance of more than 80 percent.
Drawings
FIG. 1 is a schematic diagram of a Chemical Vapor Deposition (CVD) system.
FIG. 2 is a schematic diagram of a high-temperature electrothermal fiber cloth prepared in example 1.
Fig. 3 is an SEM image of the electric heating fiber cloth prepared in example 1.
FIG. 4 is an electrical heat map of the electro-thermal fiber cloth prepared in example 1.
Fig. 5 and 6 are surface hydrophobicity characteristic display graphs of the electric heating fiber cloth prepared in example 1.
Fig. 7 is a surface air permeability characteristic display diagram of the electric heating fiber cloth prepared in example 1.
FIG. 8 is a graph showing the electrothermal performance of the electrothermal fiber cloth and the wire electrothermal film prepared in example 6.
Detailed Description
The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
The experimental procedures in the following examples are conventional unless otherwise specified. The biochemical reagents, carrier consumables and the like used in the following examples are commercially available products unless otherwise specified.
Example 1
FIG. 1 shows a conventional chemical vapor deposition apparatus with which the method of the present invention can be carried out.
The quartz fiber cloth is cleaned by adopting an ultrasonic cleaning mode, copper is coated on the surface of the quartz fiber by utilizing a method of spraying copper at normal temperature (copper nanoparticles are dissolved into a whole by utilizing a metal solvent, and a common paint spray gun is used for directly spraying a metal coating, which is an advanced technology that the prior art is not detailed here), a copper sparse structure film layer (the same below) is formed, and the thickness of the copper film is controlled to be 50 mu m (so that no metal is left in the subsequent reaction process, and the applicant finds that the fiber is easy to age and break once a catalyst is left in the fiber).
Next, the copper-coated quartz fiber cloth was placed in a high-temperature tube furnace of 1100 ℃ with a diameter of 3 inches, the internal pressure of the reaction chamber was forcibly evacuated to 10Pa or less by an oil-free vortex vacuum pump, and Ar/H was introduced21000/1000sccm, opening a toluene gas valve after the gas flow is stable, controlling the flow to be 1000sccm through toluene gas, rapidly cracking toluene vapor into activated carbon species after the toluene vapor enters the reaction cavity, adsorbing a large amount of activated carbon species to the surface of the quartz fiber, and transferring and colliding on the surface, thereby realizing the nucleation and growth of the microcrystalline graphite. The growth process of the carbon material is set to be 120 minutes, a toluene valve is quickly closed after the growth is finished, andAr/H is reacted2Set to 300/300sccm, initiate the cool down process. When the temperature in the reaction cavity is reduced to room temperature, closing Ar/H2And opening the bin to take out the sample.
The experimental results show that: the liquefied gas flame gun is adopted to carry out a heat resistance experiment on the prepared electric heating fiber cloth, and the test result shows that when the temperature is higher than 1200 ℃, the fiber cloth is brittle after being continuously heated for 5 minutes, but still has the non-combustible characteristic, which indicates that the electric heating fiber material of the embodiment can resist the high temperature of 1200 ℃; testing the sample by adopting a four-probe tester, wherein the test result is that the surface resistance value is 10 omega/sq; copper strips are attached to two ends of 4 x 4cm fiber cloth to serve as conductive electrodes, and a sample can be heated to 100 ℃ instantly (less than 1 second) by applying 3V direct current/alternating current, so that a good quick heating characteristic is presented, and a heating surface is uniform; the JCY-2 drop contact angle measuring instrument is adopted to measure the contact angle of the fiber cloth to be 100 degrees, and the fiber cloth shows the characteristic of hydrophobicity; the sample is compared before and after being in a water vapor environment at 100 ℃ to know that the sample has the air permeability. The method comprises the steps of adopting a TIR100-2 emissivity rapid tester to receive infrared radiation radiated by a hemispherical black body with the temperature of 100 ℃ on the surface of a sample to be tested, receiving the infrared radiation reflected by the sample to measure the reflectivity, obtaining the emissivity according to a calibration value, and obtaining the far infrared emissivity with the measurement result of 0.95. The sample micro-area component element species were analyzed by a German Bruker X-ray energy spectrometer (QUANTAX EDS) system, and no Cu element residue was detected. In addition, by measuring the power consumption and the heat productivity respectively, it can be determined that the electric-heat conversion efficiency is close to 100% and can reach more than 99%.
Example 2
Cleaning quartz fiber cloth by adopting an ultrasonic cleaning mode, coating copper on the surface of the quartz fiber by utilizing a magnetron sputtering method, and controlling the thickness of a copper film to be 50 mu m; putting the copper-coated quartz fiber cloth into a high-temperature tube furnace at 1100 ℃, forcibly pumping the pressure in a reaction cavity to be below 10Pa by using an oil-free vortex vacuum pump, and introducing Ar/H21000/1000sccm, opening a toluene gas valve after the gas flow is stable, controlling the flow to be 1000sccm, cracking the toluene vapor into activated carbon species after the toluene vapor enters the reaction chamber, adsorbing a large amount of activated carbon species on the surface of the quartz fiber, migrating and colliding on the surface,thereby realizing the nucleation and growth of the microcrystalline graphite. The growth process of the carbon material is set to be 120 minutes, the toluene valve is quickly closed after the growth is finished, and Ar/H is added2Set to 300/300sccm, initiate the cool down process. When the temperature in the reaction cavity is reduced to room temperature, closing Ar/H2And opening the bin to take out the sample.
The experimental results show that: the liquefied gas flame gun is adopted to carry out a heat resistance experiment on the prepared electric heating fiber cloth, and the test result shows that when the temperature is higher than 800 ℃, the fiber cloth has a brittle fracture phenomenon, which shows that the electric heating fiber material of the embodiment can resist the high temperature of 800 ℃, the experiment result is obviously reduced compared with that of the embodiment 1, and the electric heating fiber material still has the non-combustible characteristic; and testing the sample by using a four-probe tester, wherein the test result is that the surface resistance value is 10 omega/sq. The method adopts a TIR100-2 emissivity rapid tester, the surface of a tested sample receives infrared radiation radiated by a hemispherical black body at 100 ℃, the infrared radiation reflected by the sample is received to measure reflectivity, the emissivity is obtained according to a calibration value, and the measurement result is that the far infrared emissivity is 0.86, which is reduced compared with the structure in the embodiment 1. And (3) analyzing the component element types of the sample micro-area by adopting a German Bruker X-ray energy spectrometer (QUANTAX EDS) system, and detecting a small amount of Cu element residues. The applicant finds through repeated research that the bonding force between the metal copper film obtained through magnetron sputtering and the fiber surface is large, and the volatilization and diffusion of copper vapor are not facilitated in the growth process of the microcrystalline graphite, so that the copper can be remained under the same growth condition. The metallic copper is easily oxidized under high temperature conditions in the air, thereby causing the heat resistant temperature of the sample to be lowered. Meanwhile, the infrared emissivity of the metal copper is far lower than that of the microcrystalline graphite, so that the infrared emissivity of the sample 2 is reduced.
Example 3
Cleaning quartz fiber cloth by adopting an ultrasonic cleaning mode, coating nickel on the surface of the quartz fiber by utilizing a normal-temperature nickel spraying method, and controlling the thickness of a nickel film to be 30 micrometers; putting the quartz fiber coated with nickel into a high-temperature tube furnace at 400 ℃, forcibly pumping the internal pressure of a reaction cavity to be below 10Pa by using an oil-free vortex vacuum pump, and introducing Ar/H21000/1000sccm, opening the ethylene gas valve after the gas flow is stable, controlling the flow to be 1000sccm,ethylene gas is rapidly cracked into activated carbon species after entering the reaction cavity, and a large number of activated carbon species are adsorbed to the surface of the quartz fiber and migrate and collide on the surface, so that the nucleation and growth of the microcrystalline graphite are realized. The growth process of the carbon material is set to be 120 minutes, the ethylene valve is quickly closed after the growth is finished, and Ar/H is added2Set to 300/300sccm, initiate the cool down process. When the temperature in the reaction cavity is reduced to room temperature, closing Ar/H2And opening the bin to take out the sample.
The experimental results show that: the heat resistance test of the prepared electric heating fiber is carried out by adopting a liquefied gas flame gun, and the test result shows that when the temperature is higher than 1200 ℃, the fiber has a brittle fracture phenomenon and has the characteristic of non-combustibility; and (3) testing the sample 3 by using a four-probe tester, wherein the test result is that the surface resistance value is 100 omega/sq. The infrared radiation radiated by the hemispherical black body with the temperature of 100 ℃ is received by the surface of the sample to be measured by adopting a TIR100-2 emissivity rapid measuring instrument, the reflectivity is measured by receiving the infrared radiation reflected by the sample 3, the emissivity is obtained according to the calibration value, and the far infrared emissivity is 0.96 according to the measurement result. And analyzing the component element types of the sample micro-area by adopting a German Bruker X-ray energy spectrometer (QUANTAX EDS) system, and detecting no nickel element residue. The growth temperature is greatly reduced compared with that of the embodiment 1, and analysis shows that the solid solubility of carbon in nickel is high in the temperature range of 773-1573K, carbon atoms or carbon free radicals formed after the carbon source is catalytically cracked on the surface of nickel metal at high temperature enter a nickel metal substrate phase, and a thicker microcrystalline graphite layer is formed on the surface of the nickel metal phase after the temperature is reduced.
Example 4
Cleaning quartz fiber cloth by adopting an ultrasonic cleaning mode, coating nickel on the surface of the quartz fiber by utilizing a normal-temperature nickel spraying method, and controlling the thickness of a nickel film to be 30 micrometers; putting the quartz fiber coated with nickel into a high-temperature tube furnace at 300 ℃, forcibly pumping the internal pressure of a reaction cavity to be below 10Pa by using an oil-free vortex vacuum pump, and introducing Ar/H21000/1000sccm, opening a toluene gas valve after the gas flow is stable, controlling the flow to be 1000sccm, cracking the toluene gas into activated carbon species after the toluene gas enters the reaction chamber, adsorbing a large amount of activated carbon species on the surface of the quartz fiber, and transferring and colliding on the surface, thereby realizing the purposeNucleation and growth of microcrystalline graphite. The growth process of the carbon material is set to be 120 minutes, the toluene valve is quickly closed after the growth is finished, and Ar/H is added2Set to 300/300sccm, initiate the cool down process. When the temperature in the reaction cavity is reduced to room temperature, closing Ar/H2And opening the bin to take out the sample.
The experimental results show that: the heat resistance test of the prepared electric heating fiber is carried out by adopting a liquefied gas flame gun, and the test result shows that when the temperature is higher than 1200 ℃, the fiber has a brittle fracture phenomenon and has the characteristic of non-combustibility; and (3) testing the sample 4 by using a four-probe tester, wherein the test result is that the surface resistance value is 150 omega/sq. The infrared radiation radiated by the hemispherical black body with the temperature of 100 ℃ is received by the surface of the sample to be measured by adopting a TIR100-2 emissivity rapid measuring instrument, the reflectivity is measured by receiving the infrared radiation reflected by the sample 4, the emissivity is obtained according to the calibration value, and the far infrared emissivity is 0.96 according to the measurement result. And analyzing the component element types of the sample micro-area by adopting a German Bruker X-ray energy spectrometer (QUANTAX EDS) system, and detecting no nickel element residue. Compared with the sample of example 3, the growth temperature is reduced to 300 degrees, and analysis shows that the low-temperature cracking of the toluene can be realized under the condition of nickel metal catalysis, and a large amount of benzene ring free radicals exist, so that the hexagonal honeycomb-shaped carbon crystal lattice rapid stacking can be realized.
Example 5
Cleaning quartz fiber cloth by adopting an ultrasonic cleaning mode, coating nickel on the surface of the quartz fiber by utilizing a normal-temperature nickel spraying method, and controlling the thickness of a nickel film to be 10 mu m; putting the quartz fiber coated with nickel into a high-temperature tube furnace at 400 ℃, forcibly pumping the internal pressure of a reaction cavity to be below 10Pa by using an oil-free vortex vacuum pump, and introducing Ar/H21000/1000sccm, opening a toluene gas valve after the gas flow is stable, controlling the flow to be 1000sccm, quickly cracking the toluene gas into activated carbon species after the toluene gas enters the reaction cavity, adsorbing a large amount of activated carbon species onto the surface of the quartz fiber, and transferring and colliding on the surface, thereby realizing the nucleation and growth of the microcrystalline graphite. Setting the growth process of the carbon material to be 20 minutes, quickly closing a toluene valve after the growth is finished, and adding Ar/H2Set to 300/300sccm, initiate the cool down process. When the temperature in the reaction cavity is reduced to room temperature, closing Ar/H2Opening the bin and taking outAnd (3) sampling.
The experimental results show that: the heat resistance test of the prepared electric heating fiber is carried out by adopting a liquefied gas flame gun, and the test result shows that when the temperature is higher than 1200 ℃, the fiber has a brittle fracture phenomenon and has the characteristic of non-combustibility; the sample 5 was tested with a four-probe tester, and the test result was 1800 Ω/sq. The infrared radiation radiated by the hemispherical black body with the temperature of 100 ℃ is received by the surface of the sample to be measured by adopting a TIR100-2 emissivity rapid measuring instrument, the reflectivity is measured by receiving the infrared radiation reflected by the sample 5, the emissivity is obtained according to the calibration value, and the far infrared emissivity is 0.96 according to the measurement result. And analyzing the component element types of the sample micro-area by adopting a German Bruker X-ray energy spectrometer (QUANTAX EDS) system, and detecting no nickel element residue. The resistance value was increased as compared with the sample of example 4, and it was found by analysis that the thickness of the microcrystalline graphite layer on the surface of the fiber could be controlled by controlling the content and growth time of the nickel metal catalyst, and the resistance value was lower as the thickness was larger.
Example 6
Cleaning the glass fiber cloth by adopting an ultrasonic cleaning mode, coating nickel on the surface of the glass fiber by utilizing a normal-temperature nickel spraying method, and controlling the thickness of a nickel film to be 30 mu m; putting the glass fiber cloth coated with nickel into a high-temperature tube furnace at 500 ℃, forcibly pumping the internal pressure of a reaction cavity to be below 10Pa by using an oil-free vortex vacuum pump, and introducing Ar/H21000/1000sccm, opening a toluene gas valve after the gas flow is stable, controlling the flow to be 1000sccm, quickly cracking the toluene vapor into activated carbon species after the toluene vapor enters the reaction cavity, adsorbing a large amount of activated carbon species onto the surface of the quartz fiber, and transferring and colliding on the surface, thereby realizing the nucleation and growth of the microcrystalline graphite. The growth process of the carbon material is set to be 120 minutes, the toluene valve is quickly closed after the growth is finished, and Ar/H is added2Set to 300/300sccm, initiate the cool down process. When the temperature in the reaction cavity is reduced to room temperature, closing Ar/H2And opening the bin to take out the sample.
The experimental results show that: the heat resistance test of the prepared electric heating fiber cloth is carried out by adopting a liquefied gas flame gun, and the test result shows that the fiber cloth has a brittle fracture phenomenon and still has the non-combustible characteristic when the temperature is higher than 700 ℃; testing the sample by adopting a four-probe tester, wherein the test result is that the surface resistance value is 230 omega/sq; and analyzing the component element types of the sample micro-area by adopting a German Bruker X-ray energy spectrometer (QUANTAXEDS) system, and detecting no nickel element residue. And respectively taking a 2 x 2cm metal wire electrothermal film and microcrystalline graphite fiber cloth to carry out an electrothermal performance test. The test result shows that the temperature rise speed of the microcrystalline graphene fiber cloth is high, and the thermal stability is good. The thermoelectric conversion rate of the microcrystalline graphite fiber cloth is 91.4%, and the thermoelectric conversion rate of the metal wire electrothermal film is 82.1%.
Example 7
Cleaning quartz fiber cloth by adopting an ultrasonic cleaning mode, coating copper on the surface of the quartz fiber by utilizing a normal-temperature copper spraying method, and controlling the thickness of a copper film to be 1 mu m; putting the copper-coated quartz fiber into a high-temperature tube furnace at 1100 ℃, forcibly pumping the pressure in a reaction cavity to be below 10Pa by using an oil-free vortex vacuum pump, and introducing Ar/H21000/1000sccm, opening an ethylene gas valve after the gas flow is stable, controlling the flow to be 1000sccm, rapidly cracking the ethylene gas into activated carbon species after the ethylene gas enters the reaction cavity, adsorbing a large amount of activated carbon species onto the surface of the quartz fiber, and transferring and colliding on the surface, thereby realizing the nucleation and growth of the microcrystalline graphite. The growth process of the carbon material is set to be 120 minutes, the ethylene valve is quickly closed after the growth is finished, and Ar/H is added2Set to 300/300sccm, initiate the cool down process. When the temperature in the reaction cavity is reduced to room temperature, closing Ar/H2And opening the bin to take out the sample.
The experimental results show that: the heat resistance test of the prepared electric heating fiber is carried out by adopting a liquefied gas flame gun, and the test result shows that when the temperature is higher than 1200 ℃, the fiber has a brittle fracture phenomenon and has the characteristic of non-combustibility; and testing the sample 7 by using a four-probe tester, wherein the test result is that the surface resistance value is more than 10M omega/sq. The method comprises the steps of adopting a TIR100-2 emissivity rapid tester to receive infrared radiation radiated by a hemispherical black body at 100 ℃ on the surface of a tested sample, receiving the infrared radiation reflected by a sample 7 to measure reflectivity, and obtaining emissivity according to a calibration value, wherein the measurement result is that the far infrared emissivity is 0.48, and the far infrared emissivity is greatly reduced. And analyzing the component element types of the sample micro-area by adopting a German Bruker X-ray energy spectrometer (QUANTAX EDS) system, and detecting no copper element residue. Analysis shows that because the copper film is too thin, copper is volatilized rapidly under the high-temperature condition, copper steam is pumped out of the reaction cavity rapidly through vacuumizing, the concentration of the copper steam is too low, an effective catalytic effect is not achieved, carbon species particles are deposited on the surface of the fiber in an amorphous carbon mode, the resistance value of a sample 7 is increased rapidly, and the far infrared emissivity is reduced greatly.
Example 8
Cleaning quartz fiber cloth by adopting an ultrasonic cleaning mode, coating copper on the surface of the quartz fiber by utilizing a normal-temperature copper spraying method, and controlling the thickness of a copper film to be 200 mu m; putting the copper-coated quartz fiber into a high-temperature tube furnace at 1100 ℃, forcibly pumping the pressure in a reaction cavity to be below 10Pa by using an oil-free vortex vacuum pump, and introducing Ar/H21000/1000sccm, opening an ethylene gas valve after the gas flow is stable, controlling the flow to be 1000sccm, rapidly cracking the ethylene gas into activated carbon species after the ethylene gas enters the reaction cavity, adsorbing a large amount of activated carbon species onto the surface of the quartz fiber, and transferring and colliding on the surface, thereby realizing the nucleation and growth of the microcrystalline graphite. The growth process of the carbon material is set to be 120 minutes, the ethylene valve is quickly closed after the growth is finished, and Ar/H is added2Set to 300/300sccm, initiate the cool down process. When the temperature in the reaction cavity is reduced to room temperature, closing Ar/H2And opening the bin to take out the sample.
The experimental results show that: the heat resistance test of the prepared electric heating fiber is carried out by adopting a liquefied gas flame gun, and the test result shows that the fiber has a brittle fracture phenomenon and has the characteristic of non-combustibility when the temperature is higher than 600 ℃; and testing the sample 8 by using a four-probe tester, wherein the test result is the surface resistance value of 8 omega/sq. The infrared radiation radiated by the hemispherical black body with the temperature of 100 ℃ is received by the surface of the sample to be measured by adopting a TIR100-2 emissivity rapid measuring instrument, the reflectivity is measured by receiving the infrared radiation reflected by the sample 8, the emissivity is obtained according to the calibration value, and the far infrared emissivity is 0.53 as the measurement result. And (3) analyzing the component element types of the sample micro-area by adopting a German Bruker X-ray energy spectrometer (QUANTAXEDS) system, and detecting a large amount of copper element residues. Analysis shows that the copper film is too thick, so that a large amount of residues exist in the high-temperature growth process of copper, and a fiber/copper/microcrystalline graphite composite material is formed. Thereby reducing the resistance value and far infrared heating rate of the material. Meanwhile, the increase of the thickness of the copper film also increases the production cost of the material.
It should be noted that, although the above embodiments are described in the form of the electric heating fiber cloth, the present invention is not limited to the preparation of the electric heating fiber cloth, and the electric heating fiber wire, the electric heating fiber net or other configurations that the electric heating fiber can be configured to can be realized by the method of the present invention.
The above description of the specific embodiments of the present invention is not intended to limit the present invention, and those skilled in the art may make various changes and modifications according to the present invention without departing from the spirit of the present invention, which is defined by the scope of the appended claims.

Claims (7)

1. A preparation method of high-temperature-resistant electrothermal fibers is characterized by comprising the following steps:
step 1: preparing a clean fiber material, wherein the fiber material is an insulating high-temperature-resistant fiber material and is selected from at least one of single fibers, single-bundle fibers and fiber cloth;
step 2: carrying out surface coating treatment on the fiber material by adopting a normal-temperature spray or magnetron sputtering mode, wherein the coated film layer contains a carbon source cracking catalytic material, the carbon source cracking catalytic material is a metal carbon source cracking catalytic material and is a volatile material under the conditions of reaction temperature and low pressure, and the thickness of the coated film layer is 10-100 mu m;
and step 3: placing the fiber material coated with the film in a vacuum reaction cavity;
and 4, step 4: introducing protective gas and reducing gas into the vacuum reaction cavity, wherein the gas flow of the introduced protective gas is 800-1000sccm, the gas flow of the reducing gas is 800-1000sccm, and then introducing a carbon source to perform microcrystalline graphite growth, wherein the growth temperature is 300-1100 ℃;
and 5: and cooling the fiber material in the atmosphere with protective gas and reducing gas to obtain the high-temperature-resistant electric heating fiber, wherein the surface of the high-temperature-resistant electric heating fiber is provided with a microcrystalline graphite layer.
2. The method for preparing high temperature resistant electrothermal fiber according to claim 1, wherein the thickness of the coated layer is 10-60 μm.
3. The method of claim 1, wherein the shielding gas comprises an inert gas and the reducing gas comprises H2And the step 4 further comprises introducing a carbon source after the gas flows of the protective gas and the reducing gas are stabilized.
4. The method for preparing the high-temperature-resistant electrothermal fiber according to claim 1, wherein the fiber material is quartz fiber, glass fiber, asbestos fiber, metal fiber, Lawsonia fiber or ceramic fiber.
5. The method of claim 1, wherein the carbon source is at least one selected from methane, ethylene, acetylene, polyaniline, polystyrene, toluene, benzoic acid, chlorobenzene, ethanol, and acetonitrile.
6. Use of a high temperature resistant electrothermal fiber prepared by the method of any one of claims 1 to 5, comprising applying a voltage across the high temperature resistant electrothermal fiber to effect electrothermal conversion.
7. The application of claim 6, wherein the application comprises applying the high temperature resistant electrothermal fiber in a high temperature environment with or generating 200-1200 ℃ for electrothermal conversion by means of infrared radiation.
CN201910272749.4A 2019-04-04 2019-04-04 Preparation and application of high-temperature-resistant electric heating fiber Expired - Fee Related CN110022623B (en)

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