CN108682527A - Magnetic fluorinated carbon material wave absorbing agent, preparation method, application and absorbing material - Google Patents
Magnetic fluorinated carbon material wave absorbing agent, preparation method, application and absorbing material Download PDFInfo
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- CN108682527A CN108682527A CN201810445736.8A CN201810445736A CN108682527A CN 108682527 A CN108682527 A CN 108682527A CN 201810445736 A CN201810445736 A CN 201810445736A CN 108682527 A CN108682527 A CN 108682527A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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- C01G49/00—Compounds of iron
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- C01G49/08—Ferroso-ferric oxide (Fe3O4)
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Abstract
The invention belongs to absorbing material technical fields, are related to magnetic fluorinated carbon material wave absorbing agent, preparation method, application and absorbing material.The preparation method includes：Fe is first prepared in ferroferric oxide nano granules load on the carbon material3O4@carbon material composite materials, then to Fe at 0~30 DEG C3O4@carbon material composite materials carry out fluorination treatment.It is an advantage of the present invention that on the one hand, the introducing of ferroso-ferric oxide can increase the magnetism of carbon nanotube；On the other hand, ferroso-ferric oxide can improve the fluorination reaction activity of carbon nanotube, therefore the carbon fluoride nano-tube of high degree of fluorination can be prepared at a lower temperature, to advantageously reduce the dielectric constant of wave absorbing agent.Therefore magnetic carbon fluoride nano-tube has high magnetic conductivity and low dielectric constant, thus shows good impedance matching, to strong suction intensity of wave and wide suction wave frequency section, meet the requirement of novel wave-absorbing material " light, thin, strong, wide ".
Description
Technical field
The invention belongs to absorbing material technical fields, and in particular to magnetic fluorinated carbon material wave absorbing agent, preparation method, application
And absorbing material.
Background technology
It is on the one hand daily life with the continuous development of electronic science and technology and the extensive use of electronic product
Huge facility is brought, and the electromagnetic wave that another aspect electronic product generates in use also causes greatly people
Puzzlement.In life, electromagnetic wave has upset normal communication, more causes high risks to the life and health of people；In military affairs
On, making rapid progress for Radar Technology constitutes great threat to the safety of aircraft.Traditional ferromagnetic class wave absorbing agent is because of its density
Greatly, the needs of people cannot be met by absorbing the shortcomings of weak, and the efficient wave absorbing agent of Development of Novel is of great significance.Wherein,
Carbon nanotube is one-dimensional nano wire, has excellent electrical property, huge draw ratio and excellent electric conductivity make carbon receive
Mitron can reach higher conductivity level in less additive amount.Therefore, carbon nanotube has preparation is " light, thin, strong, wide " to inhale
The potentiality of wave material.
However, pure carbon nanotube is non-magnetic material, unmatched dielectric properties and magnetic property make carbon nanotube
Impedance matching performance it is bad, electromagnetic wave is easy to reflect and cannot be lost very well in carbon nano tube surface, therefore to carbon nanometer
Pipe is modified most important for the absorbing property for improving carbon nanotube.The means of common raising carbon nanotube absorbing property
It is that magnetic nano-particle is loaded in carbon nanotube or is filled in carbon nanotube pipe, by increasing magnetic components to increase
Impedance matching, to realize the promotion of absorbing property.However, simple hydridization can not realize the big of carbon nanotube absorbing property
Amplitude is promoted, and hybrid material is still based on dielectric loss in many cases, and the introducing of magnetic particle is to wave absorbing agent magnetic conductivity
Influence it is not notable, thus the impedance matching improvement of wave absorbing agent is bad.Such as Chang is by ferroso-ferric oxide and carbon nanotube
Mixing, reflection loss only have-25.9dB (Chemical Engineering Journal 285 (2016) 497-507).Cause
This, in order to advanced optimize the absorbing property of hybrid material, had been reported that by regulate and control the shape of ferroso-ferric oxide, size,
Distributed architecture and aggregated structure regulate and control electromagnetic performance to obtain superior absorbing property (ACS applied
Materials＆interfaces, 2017,9 (3)：2973-2983).However the regulation and control difficulty of magnetic particle is larger, this limitation
Its large-scale application.
In addition, directly fluorination is the effective means that carbon nanomaterial surface is modified.Generally, directly fluorination operation it is convenient, at
This cheap, significant effect is suitable for industrialized production.Currently, directly fluorination is proved to that the electric conductivity of carbon nanomaterial can be regulated and controled
Energy and dielectric properties, it has recently been found that carbon fluoride nano-tube shows better wave-absorbing effect (The compared to original carbon nanotubes
Journal of Physical Chemistry C 2018,122,6357-6367).However, due to the stone of original carbon nanotubes
Blackization degree is high, surface inertness, and effective fluorinated method of existing realization carbon nanotube generally requires up to 400 DEG C or more
Temperature (Electrochimica Acta 107 (2013) 343-349).The fluorination of carbon nanotube can be significantly improved by introducing defect
For activity to reduce the fluorination temperature of carbon nanotube, but in order to prepare the carbon fluoride nano-tube of high fluorine content, one relatively high
Fluorination temperature (such as 190-250 DEG C) be still necessary (The Journal of Physical Chemistry C
2013,117,12078-12085).On the one hand high fluorination temperature is unfavorable for large-scale industrial production, on the other hand also right
The structure of carbon nanotube causes greatly to destroy.In addition, carbon fluoride nano-tube is a kind of non-magnetic material, still as absorbing material
Based on dielectric loss, therefore the suction wave frequency section of carbon fluoride nano-tube wave absorbing agent is often relatively narrow (being less than 2GHz).These disadvantage poles
The big application for limiting carbon fluoride nano-tube.
In consideration of it, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of preparation method of magnetic fluorinated carbon material wave absorbing agent, and this method can be with
The fluorinated carbon material of high fluorine content is prepared at room temperature, simple for process, mild condition is of low cost, it is easy to accomplish
Industrialized production.
The second object of the present invention is to provide a kind of magnetic fluorinated carbon material wave absorbing agent, be prepared by the method for the invention
The magnetic fluorinated carbon material wave absorbing agent arrived has high magnetic conductivity and low dielectric constant, thus has good impedance matching
Performance, and then electromagnetic wave loss ability is excellent.
The third object of the present invention is to provide a kind of absorbing material including above-mentioned magnetic fluorinated carbon material wave absorbing agent, be somebody's turn to do
Absorbing material at least has advantage identical with above-mentioned magnetism fluorinated carbon material wave absorbing agent.
The fourth object of the present invention is to provide a kind of above-mentioned magnetic fluorinated carbon material wave absorbing agent answering in absorbing material
With.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of preparation method of magnetic fluorinated carbon material wave absorbing agent, packet
Include following steps：
Fe is first prepared in ferroferric oxide nano granules load on the carbon material3O4@carbon material composite materials, then
To the Fe at a temperature of 0~30 DEG C3O4@carbon material composite materials carry out fluorination treatment, obtain magnetic fluorinated carbon material and inhale wave
Agent.
As further preferred technical solution, the carbon material include carbon nanotube, graphene, fullerene, graphite alkene and
One or more mixtures in carbon fiber；
Preferably, the carbon material is carbon nanotube；
Preferably, the carbon nanotube includes one in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube
Kind or a variety of mixtures.
As further preferred technical solution, Fe is prepared3O4The process of@carbon material composite materials includes：
(a) trivalent iron salt is dissolved in ethylene glycol, carbon material is added and carries out ultrasonic disperse, obtains dispersion liquid；
(b) under nitrogen protection, prepared sodium acetate/ethylene glycol solution is added dropwise to the dispersion liquid obtained in step (a)
In, it is uniformly mixed, obtains mixed liquor A；
(c) mixed liquor A that step (b) obtains is then moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, heating is protected
Temperature obtains mixed liquid B；
(d) mixed liquid B that step (c) obtains is separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4@carbon
Composites.
As further preferred technical solution, the trivalent iron salt include in iron chloride, ferric nitrate and ferric sulfate at least
One kind, preferably iron chloride；
Preferably, the mass ratio of carbon material, trivalent iron salt and sodium acetate is 1：4~5：7~9；
Preferably, the total concentration for carbon material, trivalent iron salt and sodium acetate/ethylene glycol mixture A that step (b) obtains is 15
~17mg/mL；
Preferably, the mixing time in step (b) is 30~60min；
Preferably, the heating temperature in step (c) is 180~210 DEG C, and soaking time is 5~10h.
As further preferred technical solution, to the Fe3O4@carbon material composite materials carry out the process packet of fluorination treatment
It includes：
By Fe3O4@carbon material composite materials are put into fluorination reaction kettle, after nitrogen displacement, to reaction kettle at 0~30 DEG C
In be passed through Fluorine source and carry out 0.5~3h of fluorination reaction to get to magnetic fluorinated carbon material wave absorbing agent.
As further preferred technical solution, the Fluorine source is the mixed gas of inactive gas and fluorine gas；
Preferably, further include oxygen in the mixed gas；
Preferably, the inactive gas includes at least one of nitrogen, argon gas, helium and carbon dioxide gas；
Preferably, the volume fraction of fluorine gas is 5%~20% in the mixed gas；
Preferably, the volume ratio of oxygen and fluorine gas is 1~10 in the mixed gas：1.
Fluorine source is disposably passed through into reaction kettle at 0~30 DEG C after nitrogen displacement as further preferred technical solution
It is 40~80kPa to pressure, carries out 0.5~3h of fluorination reaction；
Alternatively, after nitrogen displacement, Fluorine source is continuously passed through into reaction kettle with the speed of 0.2~5L/min at 0~30 DEG C
Carry out 0.5~3h of fluorination reaction.
According to another aspect of the present invention, the present invention also provides a kind of magnetic fluorinated carbon material wave absorbing agent, use is above-mentioned
The preparation method of magnetic fluorinated carbon material wave absorbing agent be prepared.
According to another aspect of the present invention, the present invention also provides a kind of absorbing materials, including above-mentioned magnetic fluorocarbons
Material wave absorbing agent.
According to another aspect of the present invention, the present invention also provides a kind of magnetic fluorinated carbon material wave absorbing agents to inhale
Application in wave material.
Compared with prior art, the beneficial effects of the present invention are：
(1), the method for the invention, the ferriferrous oxide nano of the first carried magnetic on the carbon materials such as carbon nanotube
Grain, then fluorination reaction is carried out at 0-30 DEG C.Since the ferroso-ferric oxide loaded in advance there is catalysis to make the fluorination of carbon nanotube
With, thus the fluorination reaction of second step only need at room temperature (0-30 DEG C) can effectively carry out, thus simple process and low cost
It is honest and clean, be conducive to industrialized production.
(2)、Fe3O4The introducing of magnetic ferroferric oxide on@carbon material composite materials can increase carbon fluoride nano-tube
Magnetic loss.
(3), magnetic fluorinated carbon material wave absorbing agent provided by the invention, is made by above-mentioned preparation method, with high
Magnetic conductivity and low dielectric constant, show more excellent impedance matching performance.Thus, which has high suction wave strong
Degree and wide suction wave frequency section, the in addition advantage of its additive amount for also having its low and thin thickness.
(4), include the absorbing material of above-mentioned magnetic fluorinated carbon material wave absorbing agent, absorbing property is excellent, the addition of wave absorbing agent
Amount is few, and escapable cost can meet the requirements such as novel wave-absorbing material is light, wave-sucking performance is strong, absorption band is wide, has good
Application prospect.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is Fe3O4Wave absorbing agent (the F-Fe obtained after@CNTs fluorinations3O4@CNTs) the full spectrograms of XPS；
Fig. 2 is F-Fe3O4The F1s/XPS open score figures of@CNTs；
Fig. 3 is F-Fe3O4@CNTs compare Fe3O4The real part of permittivity and imaginary part variation diagram of@CNTs；
Fig. 4 is Fe3O4For@CNTs/ paraffin in the reflection loss figure of different-thickness, filler additive amount is 13wt%；
Fig. 5 is F-Fe3O4For@CNTs/ paraffin in the reflection loss figure of different-thickness, filler additive amount is 13wt%.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
In a first aspect, providing a kind of preparation method of magnetic fluorinated carbon material wave absorbing agent, packet at least one embodiment
Include following steps：
Fe is first prepared in ferroferric oxide nano granules load on the carbon material3O4@carbon material composite materials, then
To the Fe at a temperature of 0~30 DEG C3O4@carbon material composite materials carry out fluorination treatment, obtain magnetic fluorinated carbon material and inhale wave
Agent.
First Fe is prepared in ferroferric oxide nano granules load by the preparation method of the present invention on the carbon material3O4@carbon
Composites, then by Fe3O4@carbon material composite materials are placed in fluorination reaction kettle directly to carry out under 0~30 DEG C (room temperature)
Fluorination treatment.On the one hand, the introducing of ferroso-ferric oxide can increase the magnetism of carbon nanotube；On the other hand, ferroso-ferric oxide can
To improve the fluorination reaction activity of carbon nanotube, therefore the fluorocarbons of high degree of fluorination can be prepared at a lower temperature
Nanotube, to advantageously reduce the dielectric constant of wave absorbing agent.So that the magnetic fluorinated carbon material wave absorbing agent being prepared has
High magnetic conductivity and low dielectric constant are conducive to improve the impedance matching of wave absorbing agent, to be imitated conducive to the suction wave for increasing wave absorbing agent
Fruit.
This method is easy to operate, mild condition, environmental-friendly, and reaction is easy to control, securely and reliably；Whole preparation process is not yet
Need complicated equipment, production cost low；And raw material is easy to get, it is easy to accomplish magnetic fluorinated carbon material wave absorbing agent scale, work
The production of industry metaplasia, safe and efficient, environmentally friendly technique effect.
In a preferred embodiment, the carbon material include carbon nanotube, graphene, fullerene, graphite alkene and
One or more mixtures in carbon fiber；
Preferably, the carbon material is carbon nanotube；
Preferably, the carbon nanotube includes one in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube
Kind or a variety of mixtures.
It is understood that the carbon material of the present invention includes but not limited to carbon nanotube, graphene, fullerene, graphite alkene
With the mixture of any one or more in carbon fiber, the carbon material of similar other structures can also be used.
The carbon material is preferably carbon nanotube, below mainly by taking carbon nanotube as an example, is carried out to the preparation method of the present invention
It is further to be described in detail, it should be understood that, which is equally applicable to the other kinds of carbon materials such as graphene
Material.
Before fluorination reaction, ferroferric oxide nano granules are first loaded on the carbon nanotubes to increase the magnetic of carbon nanotube
Property, the defective bit in carbon nanotube can provide site for the attachment of ferroso-ferric oxide.In a preferred embodiment, four
The specific load step of Fe 3 O is：
(a) trivalent iron salt is dissolved in ethylene glycol, addition 100mg carbon nanotubes are simultaneously fully dispersed in Ultrasound Instrument, obtain
Dispersion liquid；Meanwhile sodium acetate being dissolved in ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, prepared sodium acetate/ethylene glycol solution is added dropwise to point obtained in step (a) dropwise
In dispersion liquid, persistently stirs 30~60min and be sufficiently mixed to liquid, obtain mixed liquor A；Typical but unrestricted, mixing time can
Think 30min, 40min, 50min or 60min；
(c) mixed liquor A that step (b) obtains is then moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 180
5~10h is kept at~210 DEG C, obtains mixed liquid B；It is typical but unrestricted, heating temperature can be 180 DEG C, 185 DEG C, 190
DEG C, 195 DEG C, 200 DEG C, 205 DEG C or 210 DEG C, the retention time can be 5h, 6h, 7h, 8h, 9h or 10h；
(d) mixed liquid B that step (c) obtains is separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4@
CNTs nanocomposites.
Wherein, the trivalent iron salt includes but not limited at least one of iron chloride, ferric nitrate and ferric sulfate, preferably
Iron chloride, further preferably FeCl3·6H2O；
The mass ratio of carbon material, trivalent iron salt and sodium acetate is 1：4~5：7~9；It is typical but unrestricted, the mass ratio
Can be 1：4：7、1：4：8、1：4：9、1：5：7、1：5：8 or 1：5：9；
The total concentration for carbon nanotube, trivalent iron salt and sodium acetate/ethylene glycol mixture A that step (b) obtains be 15~
17mg/mL；Typical but unrestricted, the total concentration of the mixed liquor can be 15mg/mL, 16mg/mL or 17mg/mL.
It should be noted that CNTs (carbon nanotubes) is carbon nanotube.
Further, to Fe3O4@CNTs nanocomposites carry out fluorination treatment process include：By Fe3O4@CNTs receive
Nano composite material is put into fluorination reaction kettle, and nitrogen displacement is carried out to fluorination reaction kettle before first time fluorination operation, then, in
It is passed through into reaction kettle Fluorine source at 0~30 DEG C and carries out 0.5~3h of fluorination reaction to get to magnetic fluorinated carbon material wave absorbing agent.
Concretely：First fluorination reaction gas reactor is evacuated, then nitrogen is filled with into fluorination reaction kettle.Preferably, this
Nitrogen replacement operator is at least in triplicate.The purpose of nitrogen displacement is that vapor that ingredient is indefinite in removing reaction vessel etc. is miscellaneous
Matter gas prevents from impacting fluorination reaction；Simultaneously convenient for the concentration of control fluorine gas, the controllability of fluorination reaction is improved.
In an embodiment of the present invention, the preparation of wave absorbing agent can be that a certain amount of fluorination mixing is passed through into reaction vessel
Gas (Fluorine source) carries out closed fluorination reaction completion.Specifically, after nitrogen displacement, 0~30 DEG C into fluorination reaction kettle it is primary
Property be passed through fluorination mixed gas to pressure be 40~80kPa, and keep 0.5~3h.It is typical but unrestricted, fluorination reaction temperature
Such as it can be 0 DEG C, 5 DEG C, 8 DEG C, 10 DEG C, 12 DEG C, 15 DEG C, 20 DEG C, 22 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 28 DEG C or 30 DEG C；The pressure
Strong for example can be 40kPa, 50kPa, 60kPa, 70kPa or 80kPa；Retention time for example can be 0.5h, 1h, 1.5h, 2h,
2.5h or 3h.
In addition, the preparation of wave absorbing agent can also be that being continually fed into fluorination mixed gas into reaction vessel is fluorinated.Tool
Body, after nitrogen displacement, fluorination mixed gas 0.5 is continuously passed through into fluorination kettle in 0~30 DEG C of speed with 0.2~5L/min
~3h.
In above-mentioned fluorination operation, fluorination mixed gas is the mixed gas of inactive gas and fluorine gas；Optionally, described
It further includes oxygen to be fluorinated mixed gas.Inactive gas is at least one in drying nitrogen, argon gas, helium and carbon dioxide gas
Kind.The volume fraction for being fluorinated fluorine gas in mixed gas is 5%~20%；Optionally, the volume ratio of oxygen and fluorine gas is 1~10：
1, preferably 0.5~3：1.
In a kind of preferred embodiment of the present invention, preparation method of the present invention can be following steps：
(a) by FeCl3·6H2O is dissolved in ethylene glycol, and addition carbon nanotube is simultaneously fully dispersed in Ultrasound Instrument；Meanwhile
Sodium acetate is dissolved in ethylene glycol, sodium acetate/ethylene glycol solution is prepared；Carbon nanotube, FeCl3·6H2O and sodium acetate
Mass ratio is 1：4~5：7~9；
(b) under nitrogen protection, sodium acetate/ethylene glycol solution that step (a) processing obtains is added dropwise dropwise in carbon nanometer
Pipe-FeCl3In/ethylene glycol dispersion liquid, persistently stirring 30~60min and be sufficiently mixed to liquid, the total concentration of mixed liquor is 15~
17mg/mL；
(c) mixed liquor that step (b) processing obtains is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 180
5~10h is kept at~210 DEG C；
(d) mixed liquor that step (c) is prepared is separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4@
CNTs nanocomposites；
(e) Fe that step (d) is prepared3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2Displacement gas
After body, it is 40~80KPa to be disposably passed through fluorination mixed gas to pressure into fluorination reaction kettle at 0~30 DEG C, and keeps 0.5
~3h；Alternatively, after nitrogen displacement, it is mixed that fluorination is continuously passed through into fluorination reaction kettle in 0~30 DEG C of speed with 0.2~5L/min
0.5~3h of gas is closed, takes out, obtains magnetic fluorinated carbon material wave absorbing agent.
The above-mentioned preparation method of wave absorbing agent, the presence of ferroso-ferric oxide, which to can be realized in room temperature, fills carbon nanotube
Divide fluorination, thus simple for process, mild condition, it is of low cost, be conducive to industrialized production.
Second aspect provides a kind of magnetic fluorinated carbon material wave absorbing agent, the magnetism fluorinated carbon material in some embodiments
Wave absorbing agent is prepared using the preparation method of above-mentioned magnetic fluorinated carbon material wave absorbing agent.
The magnetic fluorinated carbon material wave absorbing agent prepared using the above method has high magnetic loss due to the introducing of magnetic particle
Consumption；In addition the introducing of fluorine atom can reduce the dielectric constant of wave absorbing agent, thus have better impedance matching performance, to show
Go out more excellent wave-absorbing effect.
The third aspect provides a kind of absorbing material in some embodiments, including the magnetic fluorinated carbon material inhales wave
Agent.
Fourth aspect provides a kind of magnetic fluorinated carbon material wave absorbing agent in absorbing material in some embodiments
Application.
The absorbing material of the third aspect of the present invention and the application of fourth aspect, with aforementioned magnetic fluorinated carbon material wave absorbing agent
Preparation method be thus its preparation method with aforementioned magnetic fluorinated carbon material wave absorbing agent based on same inventive concept
Institute is effective, and details are not described herein.
With reference to specific embodiments and the drawings, the invention will be further described.
Embodiment 1
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 400mgFeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 700mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 30min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 5h is kept at 180 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 10
DEG C into fluorination kettle, to be disposably passed through delivery of fluorine/nitrogen mixed gas to the pressure that concentration of fluorine is 10% be 40kPa, and is kept
0.5h obtains magnetic fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 7.1at% using XPS in embodiment 1, inhales
The hysteresis loop of wave agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 37.3emu/g, coercivity 31.1Oe.
Finally obtained wave absorbing agent is scattered in paraffin, wherein the mass fraction of wave absorbing agent is 13wt%, and wave absorbing agent/paraffin is mixed
It is 7mm that object, which is pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.It utilizes vector network analyzer (Agilent E8363B)
Test the dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 2.61mm be -45dB,
Bandwidth when thickness is 2.5mm less than -10dB is 4.1GHz.
Embodiment 2
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 450mgFeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 800mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 50min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 7h is kept at 190 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 10
DEG C into fluorination kettle, to be disposably passed through delivery of fluorine/nitrogen mixed gas to the pressure that concentration of fluorine is 10% be 40kPa, and is kept
0.5h obtains magnetic fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 11at% using XPS in embodiment 2, inhales wave
The hysteresis loop of agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 31.1emu/g, coercivity 29.1Oe.It will
Finally obtained wave absorbing agent is scattered in paraffin, and wherein the mass fraction of wave absorbing agent is 13wt%, by wave absorbing agent/mineral wax mixture
It is 7mm to be pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.It is tested using vector network analyzer (AgilentE8363B)
The dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 2.32mm be -51dB, in thickness
Bandwidth when degree is 2.2mm less than -10dB is 4.4GHz.
Embodiment 3
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 500mgFeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 10
DEG C into fluorination kettle, to be disposably passed through delivery of fluorine/nitrogen mixed gas to the pressure that concentration of fluorine is 10% be 40kPa, and is kept
0.5h obtains magnetic fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 13at% using XPS in embodiment 3, inhales wave
The hysteresis loop of agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 29.1emu/g, coercivity 27.9Oe.It will
Finally obtained wave absorbing agent is scattered in paraffin, and wherein the mass fraction of wave absorbing agent is 13wt%, by wave absorbing agent/mineral wax mixture
It is 7mm to be pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.It is tested using vector network analyzer (AgilentE8363B)
The dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 2.43mm be -41dB, in thickness
Bandwidth when degree is 2.3mm less than -10dB is 3.7GHz.
Embodiment 4
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 500mgFeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 20
DEG C into fluorination kettle, to be disposably passed through delivery of fluorine/nitrogen mixed gas to the pressure that concentration of fluorine is 10% be 60kPa, and is kept
1.5h obtains magnetic fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 15.2at% using XPS in embodiment 4, inhales
The hysteresis loop of wave agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 25.4emu/g, coercivity 22.5Oe.
Finally obtained wave absorbing agent is scattered in paraffin, wherein the mass fraction of wave absorbing agent is 13wt%, and wave absorbing agent/paraffin is mixed
It is 7mm that object, which is pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.It is surveyed using vector network analyzer (AgilentE8363B)
Try the dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 2.57mm be -37dB,
Bandwidth when thickness is 2.2mm less than -10dB is 4.0GHz.
Embodiment 5
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 500mgFeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 30
DEG C into fluorination kettle, to be disposably passed through delivery of fluorine/nitrogen mixed gas to the pressure that concentration of fluorine is 10% be 80kPa, and is kept
3h obtains magnetic fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 16.5at% using XPS in embodiment 5, inhales
The hysteresis loop of wave agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 22.4emu/g, coercivity 26.8Oe.
Finally obtained wave absorbing agent is scattered in paraffin, wherein the mass fraction of wave absorbing agent is 13wt%, and wave absorbing agent/paraffin is mixed
It is 7mm that object, which is pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.It is surveyed using vector network analyzer (AgilentE8363B)
Try the dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 2.69mm be -33dB,
Bandwidth when thickness is 2.5mm less than -10dB is 3.2GHz.
Embodiment 6
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 500mgFeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 25
DEG C with the speed of 0.2L/min to fluorination kettle in be continuously passed through concentration of fluorine be 5% delivery of fluorine/nitrogen mixed gas 2h, obtain magnetic
Property fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 10.5at% using XPS in embodiment 6, inhales
The hysteresis loop of wave agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 32.3emu/g, coercivity 27Oe.It will
Finally obtained wave absorbing agent is scattered in paraffin, and wherein the mass fraction of wave absorbing agent is 13wt%, by wave absorbing agent/mineral wax mixture
It is 7mm to be pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.It is surveyed using vector network analyzer (Agilent E8363B)
Try the dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 2.4mm be -48.7dB,
Bandwidth when thickness is 2.3mm less than -10dB is 3.8GHz.
Embodiment 7
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 500mg FeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 25
DEG C with the speed of 2L/min to fluorination kettle in be continuously passed through concentration of fluorine be 10% delivery of fluorine/nitrogen mixed gas 2h, obtain magnetic
Property fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 15.8at% using XPS in embodiment 7, inhales
The hysteresis loop of wave agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 24.8emu/g, coercivity 24.2Oe.
Finally obtained wave absorbing agent is scattered in paraffin, wherein the mass fraction of wave absorbing agent is 13wt%, and wave absorbing agent/paraffin is mixed
It is 7mm that object, which is pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.It utilizes vector network analyzer (Agilent E8363B)
Test the dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 2.98mm be -34dB,
Bandwidth when thickness is 2.4mm less than -10dB is 3.7GHz.
Embodiment 8
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 500mg FeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 25
DEG C with the speed of 5L/min to fluorination kettle in be continuously passed through concentration of fluorine be 20% delivery of fluorine/nitrogen mixed gas 2h, obtain magnetic
Property fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 24at% using XPS in embodiment 8, inhales wave
The hysteresis loop of agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 19.3emu/g, coercivity 25Oe.It will most
The wave absorbing agent obtained eventually is scattered in paraffin, and wherein the mass fraction of wave absorbing agent is 13wt%, by wave absorbing agent/mineral wax mixture pressure
It is 7mm at outer diameter, internal diameter 3mm, thickness is the annulus of 3mm.It is tested using vector network analyzer (Agilent E8363B)
The dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 3.2mm be -31dB, in thickness
For 2.8mm when bandwidth less than -10dB be 3.1GHz.
Embodiment 9
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 500mg FeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 25
DEG C with the speed of 0.2L/min to fluorination kettle in be continuously passed through fluorine gas/oxygen/nitrogen mixed gas 2h, wherein oxygen, fluorine gas, nitrogen
The volume ratio of gas is 10：5：85, obtain magnetic fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 6.5at% using XPS in embodiment 9, inhales
The hysteresis loop of wave agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 34.3emu/g, coercivity 32Oe.It will
Finally obtained wave absorbing agent is scattered in paraffin, and wherein the mass fraction of wave absorbing agent is 13wt%, by wave absorbing agent/mineral wax mixture
It is 7mm to be pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.It is surveyed using vector network analyzer (Agilent E8363B)
Try the dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RLmin) in 2.3mm be -49dB, in thickness
Bandwidth when degree is 2.1mm less than -10dB is 4.3GHz.
Embodiment 10
A kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, includes the following steps：
(a) by 500mg FeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material；
(e) by the above-mentioned Fe of 50mg3O4@CNTs nanocomposites are put into fluorination reaction kettle, N2After substitution gas, 25
DEG C with the speed of 2L/min to fluorination kettle in be continuously passed through fluorine gas/oxygen/nitrogen mixed gas 2h, wherein oxygen, fluorine gas, nitrogen
Volume ratio be 5：5：90, obtain magnetic fluorinated carbon material wave absorbing agent.
The fluorine content of obtained magnetism fluorinated carbon material wave absorbing agent is measured as 11.4at% using XPS in embodiment 10,
The hysteresis loop of wave absorbing agent is measured using vibration magnetometer in room temperature, saturation magnetic moment 29.8emu/g, and coercivity is
28.4Oe.Finally obtained wave absorbing agent is scattered in paraffin, wherein the mass fraction of wave absorbing agent be 13wt%, by wave absorbing agent/
It is 7mm that mineral wax mixture, which is pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.Utilize vector network analyzer (Agilent
E8363B the dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value (RL) are testedmin) in 2.67mm
For -46.7dB, the bandwidth when thickness is 2.35mm less than -10dB is 4.6GHz.
Comparative example 1
A kind of preparation method of wave absorbing agent, includes the following steps：
(a) by 500mg FeCl3·6H2O is dissolved in 40ml ethylene glycol, 100mg carbon nanotubes is added and in Ultrasound Instrument
It is fully dispersed；Meanwhile 900mg sodium acetates being dissolved in 40ml ethylene glycol, sodium acetate/ethylene glycol solution is prepared；
(b) under nitrogen protection, above-mentioned sodium acetate/ethylene glycol solution is added dropwise dropwise in carbon nanotube-FeCl3/ second two
In alcohol dispersion liquid, persistently stirring 60min to liquid is sufficiently mixed；
(c) above-mentioned mixed liquor is moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 10h is kept at 210 DEG C；
(d) above-mentioned mixed liquor will be walked to be separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4CNTs nanometers of@is multiple
Condensation material.
As different from Example 1, it is not fluorinated in comparative example 1.
The hysteresis loop of the wave absorbing agent obtained in comparative example 1 is measured using vibration magnetometer in room temperature, and saturation magnetic moment is
37.3emu/g, coercivity 26.04Oe.Finally obtained wave absorbing agent is scattered in paraffin, wherein the mass fraction of wave absorbing agent
For 13wt%, it is 7mm that wave absorbing agent/mineral wax mixture, which is pressed into outer diameter, and internal diameter 3mm, thickness is the annulus of 3mm.Utilize vector
Network Analyzer (Agilent E8363B) tests the dielectric constant and magnetic conductivity of absorbing material, obtained minimum reflection loss value
(RLmin) in -13.5dB, wave-absorbing effect is poor.
Comparative example 2
A kind of preparation method of wave absorbing agent, includes the following steps：
50mg original carbon nanotubes are put into fluorination reaction kettle, N2It is primary in kettle to being fluorinated at 10 DEG C after substitution gas
It is 80kPa that property, which is passed through delivery of fluorine/nitrogen mixed gas to the pressure that concentration of fluorine is 10%, and keeps 2h.
As different from Example 1, ferroso-ferric oxide is not loaded on the carbon nanotubes in comparative example 2.
The fluorine content of the wave absorbing agent obtained in comparative example 2 is measured as 2.86at% using XPS, nonmagnetic.It is obtained final
To wave absorbing agent be scattered in paraffin, wherein the mass fraction of wave absorbing agent is 13wt%, wave absorbing agent/mineral wax mixture is pressed into outer
Diameter is 7mm, and internal diameter 3mm, thickness is the annulus of 3mm.It is tested using vector network analyzer (Agilent E8363B) and inhales wave
The dielectric constant and magnetic conductivity of material, obtained minimum reflection loss value (RLmin) in 1.78mm be -19dB, be in thickness
Bandwidth when 1.51mm less than -10dB is 1.3GHz.
The Fe of different ferroso-ferric oxide load capacity is first prepared in embodiment 1-103O4@CNTs nanocomposites, pass through
The magnetic carbon fluoride nano-tube wave absorbing agent of different degree of fluorination is obtained after different degrees of fluorination.
In the present invention, Fig. 1 Fe3O4Wave absorbing agent (the F-Fe obtained after@CNTs fluorinations3O4@CNTs) the full spectrograms of XPS；
Fig. 2 is F-Fe3O4The F1s/XPS open score figures of@CNTs；Fig. 3 is F-Fe3O4@CNTs compare Fe3O4The dielectric constant of@CNTs is real
Portion and imaginary part variation diagram；Fig. 4 is Fe3O4For@CNTs/ paraffin in the reflection loss figure of different-thickness, filler additive amount is 13wt%；
Fig. 5 is F-Fe3O4For@CNTs/ paraffin in the reflection loss figure of different-thickness, filler additive amount is 13wt%.Embodiment 1-10 with
Comparative example 2 compares, it can be seen that Fe3O4There are the apparent peaks F1s (such as Fig. 1 institutes in composing entirely in the XPS of sample after@CNTs fluorinations
Show), XPS fluorine spectrum shows Fe3O4Product after@CNTs fluorination mainly (as shown in Figure 2) based on the fluorine in the form of 688.8eV is covalent,
This shows that fluorine is mainly grafted on the carbon nanotubes, thus demonstrates Fe3O4There is catalytic action to the fluorination of carbon nanotube, to
Conducive to the carbon fluoride nano-tube of the high fluorine content of low temperature preparation.
In addition, the dielectric constant of hydridization sample is made to reduce (as shown in Figure 3) after fluorination, thus conducive to raising wave absorbing agent
Impedance matching, to advantageously reduce the reflection of electromagnetic wave, to show superior electromagnetic wave absorption performance.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of magnetism fluorinated carbon material wave absorbing agent, which is characterized in that include the following steps：
Fe is first prepared in ferroferric oxide nano granules load on the carbon material3O4@carbon material composite materials, then 0~
To the Fe at a temperature of 30 DEG C3O4@carbon material composite materials carry out fluorination treatment, obtain magnetic fluorinated carbon material wave absorbing agent.
2. the preparation method of magnetism fluorinated carbon material wave absorbing agent according to claim 1, which is characterized in that the carbon material
Including one or more mixtures in carbon nanotube, graphene, fullerene, graphite alkene and carbon fiber；
Preferably, the carbon material is carbon nanotube；
Preferably, the carbon nanotube include one kind in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube or
A variety of mixtures.
3. the preparation method of magnetism fluorinated carbon material wave absorbing agent according to claim 1, which is characterized in that prepare Fe3O4@
The process of carbon material composite material includes：
(a) trivalent iron salt is dissolved in ethylene glycol, carbon material is added and carries out ultrasonic disperse, obtains dispersion liquid；
(b) under nitrogen protection, prepared sodium acetate/ethylene glycol solution is added dropwise in the dispersion liquid that step (a) obtains, is stirred
It mixes uniformly mixed, obtains mixed liquor A；
(c) mixed liquor A that step (b) obtains is then moved into the hydrothermal reaction kettle of polytetrafluoroethyllining lining, heating and thermal insulation obtains
To mixed liquid B；
(d) mixed liquid B that step (c) obtains is separated by solid-liquid separation, Fe is obtained after washing, drying and grinding3O4@carbon materials
Composite material.
4. the preparation method of magnetism fluorinated carbon material wave absorbing agent according to claim 3, which is characterized in that the ferric iron
Salt includes at least one of iron chloride, ferric nitrate and ferric sulfate, preferably iron chloride；
Preferably, the mass ratio of carbon material, trivalent iron salt and sodium acetate is 1：4~5：7~9；
Preferably, the total concentration for carbon material, trivalent iron salt and sodium acetate/ethylene glycol mixture A that step (b) obtains be 15~
17mg/mL；
Preferably, the mixing time in step (b) is 30~60min；
Preferably, the heating temperature in step (c) is 180~210 DEG C, and soaking time is 5~10h.
5. the preparation method of magnetism fluorinated carbon material wave absorbing agent according to claim 1, which is characterized in that described
Fe3O4@carbon material composite materials carry out fluorination treatment process include：
By Fe3O4@carbon material composite materials are put into fluorination reaction kettle, after nitrogen displacement, are led into reaction kettle at 0~30 DEG C
Enter Fluorine source and carries out 0.5~3h of fluorination reaction to get to magnetic fluorinated carbon material wave absorbing agent.
6. the preparation method of magnetism fluorinated carbon material wave absorbing agent according to claim 5, which is characterized in that the Fluorine source is
The mixed gas of inactive gas and fluorine gas；
Preferably, further include oxygen in the mixed gas；
Preferably, the inactive gas includes at least one of nitrogen, argon gas, helium and carbon dioxide gas；
Preferably, the volume fraction of fluorine gas is 5%~20% in the mixed gas；
Preferably, the volume ratio of oxygen and fluorine gas is 1~10 in the mixed gas：1.
7. the preparation method of magnetism fluorinated carbon material wave absorbing agent according to claim 5, which is characterized in that nitrogen is replaced
Afterwards, it is 40~80kPa to be disposably passed through Fluorine source to pressure into reaction kettle at 0~30 DEG C, carries out 0.5~3h of fluorination reaction；
Alternatively, after nitrogen displacement, it is continuously passed through Fluorine source progress into reaction kettle with the speed of 0.2~5L/min at 0~30 DEG C
0.5~3h of fluorination reaction.
8. a kind of magnetism fluorinated carbon material wave absorbing agent, which is characterized in that use claim 1~7 any one of them magnetism fluorine
The preparation method for changing carbon material wave absorbing agent is prepared.
9. a kind of absorbing material, which is characterized in that include magnetic fluorinated carbon material wave absorbing agent according to any one of claims 8.
10. application of the magnetism fluorinated carbon material wave absorbing agent according to any one of claims 8 in absorbing material.
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| CN110591642A (en) * | 2019-08-21 | 2019-12-20 | 中国科学院重庆绿色智能技术研究院 | Preparation method of composite wave-absorbing material based on magnetic nanoparticles/graphene/carbon fibers |
| CN110591642B (en) * | 2019-08-21 | 2022-09-20 | 中国科学院重庆绿色智能技术研究院 | Preparation method of composite wave-absorbing material based on magnetic nanoparticles/graphene/carbon fibers |
| CN112165846A (en) * | 2020-09-21 | 2021-01-01 | 山东理工大学 | Preparation method of low-frequency efficient wave-absorbing ferroferric oxide/macroporous thin-layer carbon magnetic composite material |
| CN113373553A (en) * | 2021-07-07 | 2021-09-10 | 上海圣石生物医学科技有限公司 | Carbon-based microwave absorbing material, preparation method and health-care product |
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Application publication date: 20181019 |