CN110016803B - High-temperature-resistant electric heating fiber and application thereof - Google Patents
High-temperature-resistant electric heating fiber and application thereof Download PDFInfo
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- CN110016803B CN110016803B CN201910271815.6A CN201910271815A CN110016803B CN 110016803 B CN110016803 B CN 110016803B CN 201910271815 A CN201910271815 A CN 201910271815A CN 110016803 B CN110016803 B CN 110016803B
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention provides a high-temperature-resistant electric heating fiber which comprises a fiber inner core and a microcrystalline graphite layer coated outside the fiber inner core, wherein the fiber inner core is made of high-temperature-resistant fibers. The microcrystalline graphite layer is deposited on the surface of the fiber inner core by a chemical vapor deposition method, and the thickness of the microcrystalline graphite layer is preferably less than 10 microns. 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.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a high-temperature-resistant electric heating fiber, which expands the application of the fiber 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 method for preparing a high-temperature resistant electric heating fiber materialThe preparation method prepares the electric heating material by directly growing the microcrystalline graphite, optimizes the performance of the electric heating material and reduces the cost. 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 one aspect, the invention provides a high-temperature resistant electrothermal fiber, which comprises a fiber inner core and a microcrystalline graphite layer coated outside the fiber inner core, wherein the fiber inner core is made of high-temperature resistant fibers.
Preferably, the layer of microcrystalline graphite is deposited on the surface of the inner core of the fibre by chemical vapour deposition, preferably the layer of microcrystalline graphite has a thickness of less than 10 microns.
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.
Preferably, the fiber material is at least one selected from single fibers, single-bundle fibers and fiber cloth, and is preferably insulating high-temperature-resistant fiber.
Preferably, the carbon source cracking catalytic material is a metal carbon source cracking catalytic material, and preferably, the carbon source cracking catalytic material is a volatile material under the conditions of reaction temperature and low pressure. Preferably, the catalytic material is a metallic material of nanometer scale.
Preferably, the thickness of the applied layer is 10-100 μm, preferably less than 60 μm.
In another aspect, the present invention provides an electrical appliance having a heat generating source, wherein the electrical appliance includes a power source, at least two electrodes, and the high temperature resistant fiber of claim 1, wherein the power source is connected to the two electrodes, and the electrodes are electrically connected to different portions of the high temperature resistant fiber. The electric-heat conversion can be realized by applying voltage to the two ends of the high-temperature resistant fiber through the power supply and the electrodes, and the conversion efficiency is up to more than 99%.
In another aspect, the present invention provides a method of preparing the high temperature resistant fiber.
In another aspect, the present invention provides a use of the high temperature resistant electrothermal fiber, wherein the use includes applying a voltage across the high temperature resistant electrothermal fiber to perform electrothermal conversion, and preferably, the use includes applying the high temperature resistant electrothermal fiber to a high temperature environment having or generating 200-1200 ℃ to perform electrothermal conversion by means of infrared radiation.
On the other hand, the invention provides high-temperature-resistant electric heating fiber cloth which is characterized by comprising a fiber inner core woven by high-temperature-resistant fibers and a microcrystalline graphite layer coated on the fiber inner core.
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. The membrane layer is preferably a sparsely structured membrane layer.
In the above preparation process, step 1 may include a process of cleaning 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 intricate comparative analysis on experimental results, the applicant of the present application finally obtains 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 noticed that by spraying copper or nickel at normal temperature, controlling the thickness of the copper or nickel film layer to be 25-60 μm (preferably 40-60 μm), and combining the growth time of 80-140 minutes, the electrothermal fiber with the surface resistance value lower than 100/sq, the infrared radiance of 95%, the resistance to high temperature of 1200 ℃ and the capability of realizing instant heating can be prepared. The electrothermal fiber obtained by other methods cannot achieve such excellent performance in all aspects. For example, the magnetron sputtering method for copper spraying can result in a substantial decrease in electrical properties.
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 refractory fibers of the present invention can be implemented.
The high-temperature resistant electric heating fiber comprises a fiber inner core and a microcrystalline graphite layer coated outside the fiber inner core. An exemplary process for microcrystalline graphite cladding with fibers as the core is described in detail below.
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 metal coating can be directly sprayed out by utilizing a common paint spray gun, which is the technology that the details are not described in the prior art), a copper sparse structure film layer (the same below) of copper 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 introduced21000/1000sccAnd m, opening a toluene gas valve after the gas flow is stable, controlling the flow to be 1000sccm through toluene gas, quickly cracking toluene steam into activated carbon species after the toluene steam enters the reaction cavity, adsorbing a large number 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, 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 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; by coating with copperPutting quartz fiber cloth into a high-temperature tube furnace at 1100 ℃, 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 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
Using ultrasoundsCleaning quartz fiber cloth in an acoustic cleaning mode, coating nickel on the surface of the quartz fiber by using 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 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 (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; will cover the nickel stonePutting the quartz fiber 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, 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. 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 the toluene gas valve after the gas flow is stable, controlling the flow to be 1000sccm, and quickly controlling the toluene gas after the toluene gas enters the reaction cavityCracking into active carbon species, adsorbing a large amount of active 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. 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/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; 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 at 300/300sccm, openAnd starting a cooling 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 (4)
1. The high-temperature resistant electric heating fiber is characterized by comprising a fiber inner core and a microcrystalline graphite layer coated outside the fiber inner core, wherein the thickness of the microcrystalline graphite layer is less than 10 microns, the fiber inner core is made of insulating high-temperature resistant fiber,
wherein the microcrystalline graphite layer is coated outside the fiber layer in the following way:
step 1: preparing a cleaned fibrous material selected from at least one of an individual fiber, a single bundle of fibers;
step 2: carrying out surface coating treatment on the fiber material, wherein the coated film layer contains a carbon source cracking catalytic material, the coating thickness is 10-100 microns, 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 coating adopts a normal-temperature spray-coating or magnetron sputtering mode;
and step 3: placing the fiber material coated with the film in a vacuum reaction cavity, wherein the pressure in the reaction cavity is below 10 Pa;
and 4, step 4: introducing protective gas and reducing gas into the vacuum reaction cavity, then introducing a carbon source, and growing the microcrystalline graphite at the growth temperature of 300-1100 ℃;
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.
2. The method for preparing high temperature resistant electrothermal fiber according to claim 1, wherein the thickness of the coated layer in step 2 is 10-60 μm.
3. An electrical appliance having a heat generating source, comprising a power source, at least two electrodes and the high temperature resistant fiber of claim 1, wherein the power source is connected to the two electrodes, and the electrodes are electrically connected to different portions of the high temperature resistant fiber.
4. The high-temperature-resistant electric heating fiber cloth is characterized by comprising a reticular fiber inner core woven by insulating high-temperature-resistant fibers and a microcrystalline graphite layer coated on the fiber inner core, wherein the thickness of the microcrystalline graphite layer is less than 10 microns, the fiber inner core is made of the insulating high-temperature-resistant fibers,
wherein the microcrystalline graphite layer is coated outside the fiber layer in the following way:
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, the coating thickness is 10-100 microns, 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 coating adopts a normal-temperature spray-coating or magnetron sputtering mode;
and step 3: placing the fiber material coated with the film in a vacuum reaction cavity, wherein the pressure in the reaction cavity is below 10 Pa;
and 4, step 4: introducing protective gas and reducing gas into the vacuum reaction cavity, then introducing a carbon source, and growing the microcrystalline graphite at the growth temperature of 300-1100 ℃;
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.
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| CN110016803B (en) * | 2019-04-04 | 2019-12-20 | 碳翁(北京)科技有限公司 | High-temperature-resistant electric heating fiber and application thereof |
| CN113387676B (en) * | 2020-03-12 | 2023-03-03 | 河南克莱威纳米碳材料有限公司 | Inorganic fiber-carbon nanotube far infrared heating film and preparation method thereof |
| CN113387675B (en) * | 2020-03-12 | 2023-03-03 | 河南克莱威纳米碳材料有限公司 | Body type far infrared heating product and preparation method thereof |
| CN111588100A (en) * | 2020-07-08 | 2020-08-28 | 深圳碳美医疗有限公司 | Intelligence physiotherapy shirt that generates heat |
| CN111659025A (en) * | 2020-07-13 | 2020-09-15 | 深圳碳美医疗有限公司 | Far infrared heating physiotherapy male underpants |
| CN111657566A (en) * | 2020-07-16 | 2020-09-15 | 深圳碳美医疗有限公司 | Far infrared physiotherapy brassiere that generates heat |
| CN111659027A (en) * | 2020-07-17 | 2020-09-15 | 深圳碳美医疗有限公司 | Far infrared physiotherapy ms's pants that generate heat |
| CN111658316A (en) * | 2020-07-18 | 2020-09-15 | 深圳碳美医疗有限公司 | Far infrared physiotherapy eye-shade that generates heat |
| CN114479530A (en) * | 2022-03-07 | 2022-05-13 | 邱质彬 | High-compactness long-acting anti-corrosion coating suitable for heating surface of biomass boiler |
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| JPS6342030B2 (en) * | 1983-04-05 | 1988-08-19 | Kogyo Gijutsuin | |
| JPH05117823A (en) * | 1991-10-22 | 1993-05-14 | Takeshi Masumoto | Fiber reinforced metallic composite material |
| CN1174932C (en) * | 2001-03-27 | 2004-11-10 | 西北工业大学 | Process for preparing C-base composte material by toughening and pyrolyzing compound between graphite layers |
| CN100370055C (en) * | 2005-11-07 | 2008-02-20 | 西安交通大学 | Method for quick-speed preparing carbon/carbon composite material using heat gradient chemical gas phase infiltration |
| CN101478841B (en) * | 2008-12-31 | 2012-05-02 | 西安超码科技有限公司 | Carbon/carbon heating body preparation method for polysilicon hydrogenation furnace |
| CN201528435U (en) * | 2009-11-06 | 2010-07-14 | 陈子文 | Electrothermal element |
| US8753543B2 (en) * | 2009-12-07 | 2014-06-17 | Nanotek Instruments, Inc. | Chemically functionalized submicron graphitic fibrils, methods for producing same and compositions containing same |
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| CN102619080B (en) * | 2012-04-01 | 2014-02-26 | 东华大学 | Preparation method of graphene coating polyacrylonitrile fiber composite material |
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| CN103545521A (en) * | 2012-07-11 | 2014-01-29 | 长沙永力新能源科技有限公司 | Graphite-based carbon negative composite material in special shell structure and preparation method thereof |
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| CN105274698A (en) * | 2014-06-13 | 2016-01-27 | 四川鑫达企业集团有限公司 | High heat conduction high heatproof carbon fiber heating cloth |
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| CN110022623B (en) * | 2019-04-04 | 2020-01-10 | 碳翁(北京)科技有限公司 | Preparation and application of high-temperature-resistant electric heating fiber |
| CN110016803B (en) * | 2019-04-04 | 2019-12-20 | 碳翁(北京)科技有限公司 | High-temperature-resistant electric heating fiber and application thereof |
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