CN110022623A - A kind of preparation and application of high temperature resistant fibre electroheating - Google Patents
A kind of preparation and application of high temperature resistant fibre electroheating Download PDFInfo
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- CN110022623A CN110022623A CN201910272749.4A CN201910272749A CN110022623A CN 110022623 A CN110022623 A CN 110022623A CN 201910272749 A CN201910272749 A CN 201910272749A CN 110022623 A CN110022623 A CN 110022623A
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- Prior art keywords
- high temperature
- temperature resistant
- preparation
- fibre electroheating
- resistant fibre
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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
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- 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
Abstract
The present invention provides the preparation and application of a kind of high temperature resistant fibre electroheating, which comprises step 1: preparing clean fibrous material；Step 2: surface coating processing being carried out to the fibrous material, the film layer covered includes carbon source cracking and catalyzing material；Step 3: the fibrous material coated with film is placed in vacuum reaction chamber；Step 4: being passed through inert gas and H in Xiang Suoshu vacuum reaction chamber2, after steady air current, it is passed through carbon source, carries out micro crystal graphite growth；Step 5: in inert gas and H2Under atmosphere, cool down to the fibrous material, obtains high temperature resistant fibre electroheating.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of to prepare high temperature resistant using chemical vapour deposition technique (CVD) method
The method of fibre electroheating expands fiber in the application in electrothermal component field.
Background technique
With the rapid development of the industries such as aerospace, electron and electrician, chemical metallurgy, traffic, automobile, military project, to material
Heat processing and forming and heat treatment condition require be increasingly stringenter.Therefore, the developmental research of heating method and Novel heating material
Have become the research hotspot of material science and energy development field.
Thermo electric material is for manufacturing the heater element in various resistance heating devices.Currently, electric heating is because easily controllable
With adjust and it is free from environmental pollution, be conducive to improve product quality the advantages that and be widely used.Wherein with resistance heating
Element is the easiest as the resistance-type heating method that electric heating is converted and is widely used.Common thermo electric material includes metal electric heating
Two class of material and non-metal electrothermal material.The major defect of metal electric heating material is expensive, use condition harshness, wherein
Refractory metal thermo electric material must use in vacuum or protective atmosphere.Metal class thermo electric material is usually processed into wire spiral
Shape or waveform configuration, when energization, are easy to produce induction reactance effect and cause energy loss.Non-metal electrothermal material and metal electric heating material
Compared to having many advantages, such as that high temperature resistant, corrosion-resistant, anti-oxidant, electric conversion efficiency is high, either high-temperature heating field or in it is low
Warm heating art, non-metal electrothermal material gradually substituted metal thermo electric material.However, non-metal electric heating element passes through biscuiting
Technique and sintering process are processed into rodlike, strip, plate and U-shaped etc., can not solve that component resistance discreteness is big and mechanical property
The problems such as poor.Therefore, research and development novel high-performance thermo electric material not only has important scientific research meaning, with more weight
The practical application value wanted.
Summary of the invention
It is an object of that present invention to provide a kind of preparation method of fibre electroheating material resistant to high temperature, the present invention passes through directly raw
The method of long micro crystal graphite prepares thermo electric material, optimizes the performance of thermo electric material and reduces cost.Micro crystal graphite be carbon atom with
sp2Hybridized orbit composition hexangle type is distributed in substrate in honeycomb lattice is random, forms the carbon nanomaterial of unordered superstructure.
The far infrared transmissivity for the fibre electroheating that the present invention prepares is up to 0.95, can effectively improve thermal conversion rate, reduces power consumption；
With high temperature resistant, flexibility, easy configuration and the outstanding advantages such as resistivity is adjustable, thermal inertia is small, contacted with heated object relatively closely, heat
The advantages that conduction loss is small.The use scope of extensible tradition thermo electric material, such as household electrical appliance, electronics, medical treatment, traffic, aerospace
Etc. various fields.
Specifically, in a first aspect, the present invention provides a kind of preparation method of high temperature resistant fibre electroheating, which is characterized in that
The method includes the following steps:
Step 1: preparing clean fibrous material；
Step 2: surface coating processing being carried out to the fibrous material, the film layer covered includes carbon source cracking and catalyzing material；
Step 3: the fibrous material coated with film is placed in vacuum reaction chamber；
Step 4: being passed through protective gas and reducibility gas in Xiang Suoshu vacuum reaction chamber, then pass to carbon source, carry out micro-
Brilliant growth of graphite；
Step 5: under protective gas and reducibility gas atmosphere, cooling down to the fibrous material, obtain high temperature resistant
Fibre electroheating.
Preferably, the fibrous material is selected from least one of single fiber, single fiber-bundles, fiber cloth.
Preferably, the carbon source cracking and catalyzing material is metal carbon source cracking and catalyzing material.
Preferably, institute's coating layer with a thickness of 10-100 μm, more preferably 40-60 μm.
Preferably, the protective gas includes inert gas, and the reducibility gas includes H2, and the step 4 further includes
After the steady air current of gas and reducibility gas to be protected, it is being passed through carbon source.
Preferably, the carbon source cracking and catalyzing material is the volatile material under reaction temperature and lower pressure.
On the other hand, the present invention provides a kind of high temperature resistant fibre electroheating, which is characterized in that the high temperature resistant fibre electroheating packet
The microlite layer of ink for including fibrous layer and being coated on outside the fibrous layer.
Preferably, the microlite layer of ink is coated on outside the fibrous layer by following manner:
Step 1: preparing clean fibrous material；
Step 2: surface coating processing being carried out to the fibrous material, the film layer covered includes carbon source cracking and catalyzing material；
Step 3: the fibrous material coated with film is placed in vacuum reaction chamber；
Step 4: being passed through protective gas and reducibility gas in Xiang Suoshu vacuum reaction chamber, then pass to carbon source, carry out micro-
Brilliant growth of graphite；
Step 5: under protective gas and reducibility gas atmosphere, cooling down to the fibrous material, obtain high temperature resistant
Fibre electroheating.
On the other hand, the present invention provides a kind of application of high temperature resistant fibre electroheating, and the application is included in described resistance to
High-temperature electric heat fiber both ends apply voltage, to carry out electric heating conversion.
Preferably, the application includes that the high temperature resistant fibre electroheating is Celsius applied to having or generating 200-1200
In the hot environment of degree, electric heating conversion is carried out in a manner of infra-red radiation.
Step 1 may include the process cleaned to fiber: fiber is sequentially placed into hexamethylene, ethyl alcohol, deionized water
Middle ultrasonic cleaning 10 minutes, with being dried with nitrogen, completes the cleaning of fiber.
In the step, the fiber can selected from quartz fibre resistant to high temperature, glass fibre, asbestos fibre, metallic fiber,
Nitrogen man boron fibre, ceramic fibre etc. can be at least one of 300 DEG C of fibers used above.That is, selected fiber is insulation
Refractory fibrous material.
Coating process in step 2 preferably carries out covering metal processing by covering smithcraft, and thickness of metal film is not more than
100μm。
In the step, the coating metal has at least one in the metal for being catalyzed carbon source cracking selected from copper, nickel, platinum etc.
Kind.Also, appended film layer needs to meet the pressure strip in 300 DEG C -1100 DEG C of temperature condition and step 4 in reaction process
There is volatilization effect under part.
In the step, the smithcraft of covering is selected from plating, chemical plating, sol-gel, magnetron sputtering, directly sprays gold
Belong at least one of coating.
That be passed through in step 4 into reaction chamber can be 800-1000sccm Ar and 800-1000 sccm H2.When growth
Between can control at 10-300 minutes, preferably 40-300 minutes, growth technique is set as 300 DEG C -1100 DEG C, thus covering metal
Fiber surface forms the controllable microlite layer of ink of thickness.
In the step, the carbon source is selected from gaseous state (methane, ethylene, acetylene), solid-state (polyaniline, polystyrene, etc.), liquid
At least one of state (toluene, benzoic acid, chlorobenzene, ethyl alcohol, acetonitrile etc.) carbon source.
Step 5 specifically includes: after micro crystal graphite is grown, closing carbon source steam, sets Ar and H2 flow distribution to
100-300sccm/100-300sccm starts temperature-fall period, and temperature, which is cooled to room temperature, closes Ar/H2, and sample is taken out, is completed
Whole preparation process.
Reaction temperature, various gas flows involved by above-mentioned preparation process, reaction time can be according to technique need
It is adjusted.
By the way that many experiments, and the complicated comparative analysis of carry out to experimental result is repeated, the application's
Applicants have discovered that high far infrared transmissivity, low areal resistance value, fibre electroheating preparation method resistant to high temperature may be implemented in one kind, it can
To realize resistance to 1200 degree of high temperature, realize surface resistance lower than 100 Ω/sq (even down to 10 Ω/sq in embodiment 1), infrared spoke
Rate is penetrated higher than 90%, basically reaches 95% or more preparation method (corresponding preferred embodiment of the invention).
Specifically, applicant have observed that, copper or nickel are sprayed by using room temperature, control copper or nickel thicknesses of layers in 25-
60 μm (preferably 40-60 μm), in conjunction with 80-140 minutes growth times, surface resistance can be prepared lower than 100/sq, infrared
The fibre electroheating of radiance 95%, resistance to 1200 degree of high temperature.And use other modes fibre electroheating obtained can not be in each side
Face all reaches so excellent performance.
Fibre electroheating in the present invention is due to using median fiber silk, and outside coats the construction of micro crystal graphite, compared to carbon
Fiber-like thermo electric material can not only increase toughness, the gas permeability of fibre electroheating, can also improve heat radiation area, Jin Erjin
One step improves thermal conversion efficiency, and the electric conversion efficiency close to 100% may be implemented.
Method of the invention is at low cost, high yield rate and the fibre electroheating prepared have good hydrophobic air permeable
Etc. performances, have huge social value and economic value.
Even suboptimum embodiment, method of the invention can also prepare resistance to 500 degree or more high temperature, infrared emittances
Reach 80% or more fibre electroheating material.
Detailed description of the invention
Fig. 1 is chemical vapor deposition (CVD) system schematic.
Fig. 2 is the pictorial diagram that embodiment 1 prepares high-temperature electric heat fiber cloth.
Fig. 3 is the SEM figure of fibre electroheating cloth prepared by embodiment 1.
Fig. 4 is fibre electroheating cloth electric heating figure prepared by embodiment 1.
Fig. 5,6 be the surface hydrophobicity characterization figure of fibre electroheating cloth prepared by embodiment 1.
Fig. 7 is the surface ventilating performance display diagram of fibre electroheating cloth prepared by embodiment 1.
Fig. 8 is fibre electroheating cloth and wire electrothermal film electric hot property curve graph prepared by embodiment 6.
Specific embodiment
The present invention is described below with reference to specific embodiments.It will be appreciated by those skilled in the art that these embodiments are only
For illustrating the present invention, do not limit the scope of the invention in any way.
Experimental method in following embodiments is unless otherwise specified conventional method.Life as used in the following examples
Change reagent, carrier consumptive material etc. is commercially available products unless otherwise specified.
Embodiment 1
Fig. 1 gives the equipment of conventional chemical vapor, and method of the invention can be realized using the equipment.
Quartz fiber cloth is cleaned up using ultrasonic cleaning mode, (copper is received using metal solvent using room temperature spray copper
Rice corpuscles is molten to be integrated, and with common paint sprayer, can directly spray the advanced technology of metal coating, this for the prior art here
No longer be described in detail) method in quartz fiber surface copper-clad, form the sparsity structure film layer (similarly hereinafter) of copper, control copper film thickness is 50
μm (so that metal noresidue during subsequent reactions, once it is found by the applicant that there is catalyst residual to will appear fibre in fiber
The case where tieing up fracture easy to aging).
Next, the quartz fiber cloth for covering copper is put into 1100 DEG C of the high temperature process furnances that diameter is 3 inches, nothing is utilized
Pressure in reaction chamber is evacuated to 10Pa hereinafter, being passed through Ar/H by oily scroll vacuum pump21000/1000sccm, air-flow are steadily opened afterwards
Flow control is 1000sccm by toluene gas by toluene gas valve, and toluene vapor is cracked into rapidly after entering reaction chamber
Active carbon species, a large amount of activity carbon species are adsorbed onto quartz fiber surface, in surface migration, collision, to realize micro crystal graphite
Nucleation and growth.Carbon material growth course is set as 120 minutes, closes toluene valve after growth rapidly, and by Ar/H2
It is set as 300/300sccm, opens temperature-fall period.Cavity temperature to be reacted is down to room temperature, closes Ar/H2, open a position and take out sample.
The results showed that carrying out heat resistance experiment, test knot using fibre electroheating cloth of the liquefied gas flame gun to preparation
Fruit is when temperature is greater than 1200 DEG C, and after five minutes, embrittlement phenomenon just occurs to continuous high temperature in fiber cloth, but still has non-ignitable spy
Property, illustrate that the fibre electroheating material of the present embodiment can be resistant to 1200 DEG C of high temperature；Sample is surveyed using four-point probe
Examination, test result is that surface resistance is 10 Ω/sq；The fiber cloth both ends of 4*4cm are attached into copper bar as conductive electrode, are passed through
Apply the DC/AC electricity of 3V, sample instants (less than 1 second) can be heated to 100 DEG C, show preferable speed heat characteristic, heating surface
Uniformly；, use JCY-2 drop contact angle measurement measurement fiber cloth contact angle for 100 degree, show hydrophobic characteristic；By sample
Product sample known to the comparison of front and back in 100 DEG C of water vapor atmospheres has ventilating performance.It is quickly measured using TIR 100-2 emissivity
Sample surface is received the infra-red radiation that 100 DEG C of hemispherical black body radiations go out by instrument, and the infra-red radiation of sample reflection is received
It measures reflectivity and emissivity is obtained according to calibration value, measurement result is far infrared transmissivity 0.95.Using German Brooker X
Gamma ray spectrometer (QUANTAX EDS) system analyzes sample micro-area composition element species, does not detect that Cu element remains.Separately
Outside, it is measured respectively by offseting power consumption and calorific value, it may be determined that its electric conversion efficiency is close to 100%, Ke Yida
To 99% or more.
Embodiment 2
Quartz fiber cloth is cleaned up using ultrasonic cleaning mode, using the method for magnetron sputtering in quartz fiber surface
Copper-clad, control copper film thickness are 50 μm；The quartz fiber cloth for covering copper is put into 1100 DEG C of high temperature process furnances, utilizes oil-free whirlpool
It revolves vacuum pump and pressure in reaction chamber is evacuated to 10Pa hereinafter, being passed through Ar/H21000/1000sccm, air-flow steadily open toluene afterwards
Flow control is 1000sccm by gas valve, and toluene vapor, which enters, is cracked into rapidly active carbon species after reaction chamber, largely
Active carbon species are adsorbed onto quartz fiber surface, in surface migration, collision, to realize the nucleation and growth of micro crystal graphite.Carbon
Material growth process is set as 120 minutes, closes toluene valve after growth rapidly, and by Ar/H2It is set as 300/
300sccm opens temperature-fall period.Cavity temperature to be reacted is down to room temperature, closes Ar/H2, open a position and take out sample.
The results showed that carrying out heat resistance experiment, test knot using fibre electroheating cloth of the liquefied gas flame gun to preparation
Fruit is when temperature is greater than 800 DEG C, and embrittlement phenomenon occurs in fiber cloth, illustrates that the fibre electroheating material of the present embodiment can be resistant to 800
DEG C high temperature, the experimental result compared with embodiment 1 decreased significantly, but still have non-ignitable characteristic；Using four-point probe to sample
Product are tested, and test result is that surface resistance is 10 Ω/sq.Using TIR 100-2 emissivity Quick testing instrument, by detected sample
Product surface receives the infra-red radiation that 100 DEG C of hemispherical black body radiations go out, and the infra-red radiation of sample reflection, which is received, measures reflectivity
And emissivity is obtained according to calibration value, measurement result is that far infrared transmissivity 0.86 is dropped compared with the structure in embodiment 1
It is low.Sample micro-area composition element species are analyzed using German Brooker X-ray energy spectrometer (QUANTAX EDS) system, detection
A small amount of Cu element residual out.Applicant is by repeatedly the study found that the copper metal film and fiber surface that are obtained by magnetron sputtering
Binding force it is larger, micro crystal graphite growth during, be unfavorable for the volatilization and diffusion of copper steam, therefore, identical growth item
Under part, the phenomenon that copper will appear residual.Metallic copper is easily oxidized under conditions of high temperature in air, so as to cause the heat-resisting temperature of sample
Degree decline.Meanwhile under the infrared emittance of metallic copper is well below micro crystal graphite, therefore the far infrared transmissivity of sample 2 occurs
The phenomenon that drop.
Embodiment 3
Quartz fiber cloth is cleaned up using ultrasonic cleaning mode, using the method for room temperature spray nickel in quartz fiber surface
Nickel coat, control nickel film thickness are 30 μm；The quartz fibre for covering nickel is put into 400 DEG C of high temperature process furnances, utilizes oil-free scroll
Pressure in reaction chamber is evacuated to 10Pa hereinafter, being passed through Ar/H by vacuum pump21000/1000sccm, air-flow steadily open ethylene afterwards
Flow control is 1000 sccm by gas valve, and ethylene gas, which enters, is cracked into rapidly active carbon species after reaction chamber, a large amount of living
Property carbon species be adsorbed onto quartz fiber surface, surface migration, collision, to realize the nucleation and growth of micro crystal graphite.Carbon materials
Material growth course is set as 120 minutes, closes ethylene valve after growth rapidly, and by Ar/H2It is set as 300/
300sccm opens temperature-fall period.Cavity temperature to be reacted is down to room temperature, closes Ar/H2, open a position and take out sample.
The results showed that carrying out heat resistance experiment, test result using fibre electroheating of the liquefied gas flame gun to preparation
For when temperature is greater than 1200 DEG C, there is embrittlement phenomenon in fiber, has non-ignitable characteristic；Using four-point probe to sample 3
It is tested, test result is that surface resistance is 100 Ω/sq.Using TIR 100-2 emissivity Quick testing instrument, by detected sample
Product surface receives the infra-red radiation that 100 DEG C of hemispherical black body radiations go out, and the infra-red radiation that sample 3 reflects, which is received, measures reflectivity
And emissivity is obtained according to calibration value, measurement result is far infrared transmissivity 0.96.Using German Brooker X-ray energy spectrometer
(QUANTAX EDS) system analyzes sample micro-area composition element species, does not detect that nickel element remains.Significantly compared with embodiment 1
Growth temperature is reduced, through analyzing it is found that carbon solid solubility in nickel is higher, carbon source in the K temperature range of T=773~1573
The carbon atom or carbon radicals formed after the catalytic pyrolysis of nickel metal surface under the high temperature conditions can enter nickel metallic substrates body
Xiangli, cooling Shi Zaicong nickel metallic object mutually precipitate into surface and form thicker microlite layer of ink.
Embodiment 4
Quartz fiber cloth is cleaned up using ultrasonic cleaning mode, using the method for room temperature spray nickel in quartz fiber surface
Nickel coat, control nickel film thickness are 30 μm；The quartz fibre for covering nickel is put into 300 DEG C of high temperature process furnances, utilizes oil-free scroll
Pressure in reaction chamber is evacuated to 10Pa hereinafter, being passed through Ar/H by vacuum pump21000/1000sccm, air-flow steadily open toluene afterwards
Flow control is 1000 sccm by gas valve, and toluene gas, which enters, is cracked into rapidly active carbon species after reaction chamber, a large amount of living
Property carbon species be adsorbed onto quartz fiber surface, surface migration, collision, to realize the nucleation and growth of micro crystal graphite.Carbon materials
Material growth course is set as 120 minutes, closes toluene valve after growth rapidly, and by Ar/H2It is set as 300/
300sccm opens temperature-fall period.Cavity temperature to be reacted is down to room temperature, closes Ar/H2, open a position and take out sample.
The results showed that carrying out heat resistance experiment, test result using fibre electroheating of the liquefied gas flame gun to preparation
For when temperature is greater than 1200 DEG C, there is embrittlement phenomenon in fiber, has non-ignitable characteristic；Using four-point probe to sample 4
It is tested, test result is that surface resistance is 150 Ω/sq.Using TIR 100-2 emissivity Quick testing instrument, by detected sample
Product surface receives the infra-red radiation that 100 DEG C of hemispherical black body radiations go out, and the infra-red radiation that sample 4 reflects, which is received, measures reflectivity
And emissivity is obtained according to calibration value, measurement result is far infrared transmissivity 0.96.Using German Brooker X-ray energy spectrometer
(QUANTAX EDS) system analyzes sample micro-area composition element species, does not detect that nickel element remains.Compared with 3 sample of embodiment,
Growth temperature is down to 300 °, through analysis it is found that under conditions of nickel metal catalytic but realizing low temperature pyrolyzer by control toluene,
And there are a large amount of phenyl ring free radical, it can be achieved that hexangle type is quickly stacked in honeycomb carbon lattice.
Embodiment 5
Quartz fiber cloth is cleaned up using ultrasonic cleaning mode, using the method for room temperature spray nickel in quartz fiber surface
Nickel coat, control nickel film thickness are 10 μm；The quartz fibre for covering nickel is put into 400 DEG C of high temperature process furnances, utilizes oil-free scroll
Pressure in reaction chamber is evacuated to 10Pa hereinafter, being passed through Ar/H by vacuum pump21000/1000sccm, air-flow steadily open toluene gas afterwards
Flow control is 1000 sccm by body valve, and toluene gas, which enters, is cracked into rapidly active carbon species after reaction chamber, a large amount of activity
Carbon species are adsorbed onto quartz fiber surface, in surface migration, collision, to realize the nucleation and growth of micro crystal graphite.Carbon material
Growth course is set as 20 minutes, closes toluene valve after growth rapidly, and by Ar/H2It is set as 300/300sccm, is opened
Open temperature-fall period.Cavity temperature to be reacted is down to room temperature, closes Ar/H2, open a position and take out sample.
The results showed that carrying out heat resistance experiment, test result using fibre electroheating of the liquefied gas flame gun to preparation
For when temperature is greater than 1200 DEG C, there is embrittlement phenomenon in fiber, has non-ignitable characteristic；Using four-point probe to sample 5
It is tested, test result is that surface resistance is 1800 Ω/sq.Using TIR 100-2 emissivity Quick testing instrument, by detected sample
Product surface receives the infra-red radiation that 100 DEG C of hemispherical black body radiations go out, and the infra-red radiation that sample 5 reflects, which is received, measures reflectivity
And emissivity is obtained according to calibration value, measurement result is far infrared transmissivity 0.96.Using German Brooker X-ray energy spectrometer
(QUANTAX EDS) system analyzes sample micro-area composition element species, does not detect that nickel element remains.Compared with 4 sample of embodiment,
Resistance value increases, and through analysis it is found that passing through the content and growth time of control nickel-metal catalyst, it is micro- to can control fiber surface
The thickness of spar layer of ink, thickness is bigger, and resistance value is lower.
Embodiment 6
Glass fabric is cleaned up using ultrasonic cleaning mode, using room temperature spray nickel method in fiberglass surfacing packet
Nickel, control nickel film thickness are 30 μm；The glass fabric for covering nickel is put into 500 DEG C of high temperature process furnances, utilizes oil-free scroll
Pressure in reaction chamber is evacuated to 10Pa hereinafter, being passed through Ar/H by vacuum pump21000/1000sccm, air-flow steadily open toluene afterwards
Flow control is 1000 sccm by gas valve, and toluene vapor, which enters, is cracked into rapidly active carbon species after reaction chamber, largely
Active carbon species are adsorbed onto quartz fiber surface, in surface migration, collision, to realize the nucleation and growth of micro crystal graphite.Carbon
Material growth process is set as 120 minutes, closes toluene valve after growth rapidly, and by Ar/H2It is set as 300/
300sccm opens temperature-fall period.Cavity temperature to be reacted is down to room temperature, closes Ar/H2, open a position and take out sample.
The results showed that carrying out heat resistance experiment, test knot using fibre electroheating cloth of the liquefied gas flame gun to preparation
Fruit is when temperature is greater than 700 DEG C, and embrittlement phenomenon occurs in fiber cloth, but still has non-ignitable characteristic；Using four-point probe
Sample is tested, test result is that surface resistance is 230 Ω/sq；Using German Brooker X-ray energy spectrometer (QUANTAX
EDS) system analyzes sample micro-area composition element species, does not detect that nickel element remains.The wire electric heating of 2*2cm is taken respectively
Film and micro crystal graphite fiber cloth carry out electric heating property test.Test result shows that micro crystal graphite alkene fiber cloth heating rate is fast, and
Thermal stability is good.By calculating it is found that the thermoelectric conversion rate of micro crystal graphite fiber cloth is 91.4%, the heat of wire Electric radiant Heating Film
Electrotransformation rate is 82.1%.
Embodiment 7
Quartz fiber cloth is cleaned up using ultrasonic cleaning mode, using the method for room temperature spray copper in quartz fiber surface
Copper-clad, control copper film thickness are 1 μm；The quartz fibre for covering nickel is put into 1100 DEG C of high temperature process furnances, utilizes oil-free scroll
Pressure in reaction chamber is evacuated to 10Pa hereinafter, being passed through Ar/H by vacuum pump21000/1000sccm, air-flow steadily open ethylene afterwards
Flow control is 1000 sccm by gas valve, and ethylene gas, which enters, is cracked into rapidly active carbon species after reaction chamber, a large amount of living
Property carbon species be adsorbed onto quartz fiber surface, surface migration, collision, to realize the nucleation and growth of micro crystal graphite.Carbon materials
Material growth course is set as 120 minutes, closes ethylene valve after growth rapidly, and by Ar/H2It is set as 300/
300sccm opens temperature-fall period.Cavity temperature to be reacted is down to room temperature, closes Ar/H2, open a position and take out sample.
The results showed that carrying out heat resistance experiment, test result using fibre electroheating of the liquefied gas flame gun to preparation
For when temperature is greater than 1200 DEG C, there is embrittlement phenomenon in fiber, has non-ignitable characteristic；Using four-point probe to sample 7
It is tested, test result is that surface resistance is greater than 10M Ω/sq.Using TIR 100-2 emissivity Quick testing instrument, will be tested
Sample surfaces receive the infra-red radiation that 100 DEG C of hemispherical black body radiations go out, and the infra-red radiation that sample 7 reflects, which is received, measures reflection
Rate simultaneously obtains emissivity according to calibration value, and measurement result is that far infrared transmissivity 0.48, far infrared transmissivity is greatly lowered.
Sample micro-area composition element species are analyzed using German Brooker X-ray energy spectrometer (QUANTAX EDS) system, are not detected
Copper residual.Through analysis it is found that copper volatilizees rapidly under the high temperature conditions since copper film thickness is too thin, and by vacuumize by
Copper steam detaches rapidly reaction cavity, and copper vapour concentration is too low, does not open effective catalytic effect, causes carbon species particle with nothing
The form of sizing carbon is deposited on fiber surface, and therefore, the resistance value of sample 7 increased dramatically, and far infrared transmissivity is greatly reduced.
Embodiment 8
Quartz fiber cloth is cleaned up using ultrasonic cleaning mode, using the method for room temperature spray copper in quartz fiber surface
Copper-clad, control copper film thickness are 200 μm；The quartz fibre for covering copper is put into 1100 DEG C of high temperature process furnances, utilizes oil-free whirlpool
It revolves vacuum pump and pressure in reaction chamber is evacuated to 10Pa hereinafter, being passed through Ar/H21000/1000sccm, air-flow steadily open ethylene afterwards
Flow control is 1000sccm by gas valve, and ethylene gas, which enters, is cracked into rapidly active carbon species after reaction chamber, a large amount of activity
Carbon species are adsorbed onto quartz fiber surface, in surface migration, collision, to realize the nucleation and growth of micro crystal graphite.Carbon material
Growth course is set as 120 minutes, closes ethylene valve after growth rapidly, and by Ar/H2300/300sccm is set as,
Open temperature-fall period.Cavity temperature to be reacted is down to room temperature, closes Ar/H2, open a position and take out sample.
The results showed that carrying out heat resistance experiment, test result using fibre electroheating of the liquefied gas flame gun to preparation
For when temperature is greater than 600 DEG C, there is embrittlement phenomenon in fiber, has non-ignitable characteristic；Using four-point probe to sample 8 into
Row test, test result are 8 Ω of surface resistance/sq.Using TIR 100-2 emissivity Quick testing instrument, by sample surface
The infra-red radiation that 100 DEG C of hemispherical black body radiations go out is received, the infra-red radiation that sample 8 reflects, which is received, measures reflectivity and basis
Calibration value obtains emissivity, and measurement result is far infrared transmissivity 0.53.Using German Brooker X-ray energy spectrometer
(QUANTAX EDS) system analyzes sample micro-area composition element species, detects a large amount of copper residuals.Through analysis it is found that
Since copper film thickness is too thick, there is a large amount of residual in the process of high growth temperature in copper, forms fiber/copper/micro crystal graphite and answers
Condensation material.Therefore the resistance value and far infrared heating rate of material are reduced.Meanwhile the increase of copper film thickness also increases the life of material
Produce cost.
It should be noted that, although be the description carried out with the situation of fibre electroheating cloth in above-described embodiment, but this
Invention is not limited only to the preparation of fibre electroheating cloth, fibre electroheating silk, fibre electroheating net or fibre electroheating can constitute other
Construction can be realized by means of the present invention.
Specific description of embodiments of the present invention above is not intended to limit the present invention, and those skilled in the art can be according to this
Invention is variously modified or deforms, and as long as it does not depart from the spirit of the invention, should belong to the model of appended claims of the present invention
It encloses.
Claims (10)
1. a kind of preparation method of high temperature resistant fibre electroheating, which is characterized in that the method includes the following steps:
Step 1: preparing clean fibrous material；
Step 2: surface coating processing being carried out to the fibrous material, the film layer covered includes carbon source cracking and catalyzing material；
Step 3: the fibrous material coated with film is placed in vacuum reaction chamber；
Step 4: being passed through protective gas and reducibility gas in Xiang Suoshu vacuum reaction chamber, then pass to carbon source, carry out microlite
Ink growth；
Step 5: under protective gas and reducibility gas atmosphere, cooling down to the fibrous material, obtain high temperature resistant electric heating
Fiber.
2. the preparation method of high temperature resistant fibre electroheating according to claim 1, which is characterized in that the fibrous material is selected from
At least one of single fiber, single fiber-bundles, fiber cloth.
3. the preparation method of high temperature resistant fibre electroheating according to claim 1, which is characterized in that the carbon source cracking and catalyzing
Material is metal carbon source cracking and catalyzing material.
4. the preparation method of high temperature resistant fibre electroheating according to claim 1, which is characterized in that institute's coating layer with a thickness of
10-100 μm, preferably smaller than 60 μm.
5. the preparation method of high temperature resistant fibre electroheating according to claim 4, which is characterized in that the protective gas includes
Inert gas, the reducibility gas include H2, the step 4 further includes the steady air current of gas and reducibility gas to be protected
Afterwards, then it is passed through carbon source.
6. the preparation method of high temperature resistant fibre electroheating according to claim 1, which is characterized in that the carbon source cracking and catalyzing
Material is the volatile material under reaction temperature and lower pressure.
7. the preparation method of high temperature resistant fibre electroheating according to claim 1, which is characterized in that the fibrous material is exhausted
Edge high-temperature fibre.
8. the preparation method of high temperature resistant fibre electroheating according to claim 1, which is characterized in that the carbon source is selected from first
At least one of alkane, ethylene, acetylene, polyaniline, polystyrene, toluene, benzoic acid, chlorobenzene, ethyl alcohol, acetonitrile.
9. a kind of application of the high temperature resistant fibre electroheating of any one of claim 1-8 the method preparation, the application packet
It includes and applies voltage at high temperature resistant fibre electroheating both ends, to carry out electric heating conversion, it is preferable that the application includes will be described resistance to
High-temperature electric heat fiber applications carry out electric heating in having or generating in 200-1200 degrees Celsius of hot environment in a manner of infra-red radiation
Conversion.
10. a kind of high-temperature fibre of any one of claim 1-8 the method preparation.
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| CN201910272749.4A CN110022623B (en) | 2019-04-04 | 2019-04-04 | Preparation and application of high-temperature-resistant electric heating fiber |
| PCT/CN2019/091444 WO2020199353A1 (en) | 2019-04-04 | 2019-06-16 | Preparation and use of high temperature resistant electrothermal fiber |
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| CN201910272749.4A CN110022623B (en) | 2019-04-04 | 2019-04-04 | Preparation and application of high-temperature-resistant electric heating fiber |
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| CN110022623B CN110022623B (en) | 2020-01-10 |
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| WO2020199354A1 (en) * | 2019-04-04 | 2020-10-08 | 碳翁(北京)科技有限公司 | High-temperature-resistant electrothermal fiber and application thereof |
| 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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| CN110022623B (en) | 2020-01-10 |
| WO2020199353A1 (en) | 2020-10-08 |
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