CN107163912A - A kind of MWCNTSWave absorbing agent, its preparation method and absorbing material - Google Patents
A kind of MWCNTSWave absorbing agent, its preparation method and absorbing material Download PDFInfo
- Publication number
- CN107163912A CN107163912A CN201710442184.0A CN201710442184A CN107163912A CN 107163912 A CN107163912 A CN 107163912A CN 201710442184 A CN201710442184 A CN 201710442184A CN 107163912 A CN107163912 A CN 107163912A
- Authority
- CN
- China
- Prior art keywords
- fluorination
- gas
- absorbing material
- absorbing
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention provides a kind of MWCNTs wave absorbing agents, its preparation method and absorbing material, belongs to absorbing material technical field.The preparation method of wave absorbing agent includes:First time fluorination is carried out to multi-walled carbon nanotube at a temperature of 0 30 DEG C, then carrying out second to multi-walled carbon nanotube at a temperature of 100 190 DEG C is fluorinated.Realize outer tube is fully fluorinated while can protection inner tube it is without damage;Only need to be fluorinated operation twice, technique is simple, with low cost, beneficial to industrialized production.Wave absorbing agent is made using this method, and fluorination impedance matching layer is formed in CNT outer layer by being directly fluorinated growth in situ, and structural stability is preferable, beneficial to the transmission of electromagnetic wave;The integrality of inner tube is good, and electromagnetic wave loss ability is excellent.Absorbing material includes resin material and above-mentioned wave absorbing agent, and absorbing property and mechanical performance are excellent, meet the requirement of novel wave-absorbing material " light, thin, strong, width ".
Description
Technical field
The present invention relates to absorbing material technical field, in particular to a kind of MWCNTs wave absorbing agents, its preparation method and
Absorbing material.
Background technology
Scientific and technical continues to develop so that various electronic products, electric equipment are lived in people and military field is obtained
It is widely applied.In daily life, on the one hand, electronic equipment is that people's life is provided a great convenience;And on the other hand,
The electromagnetic pollution that electronic equipment is produced during utilization also significantly impacts the life of people, such as electromagnetic radiation has been upset just
Normal communication, the more life and health to human body cause grave danger.Militarily, it is traditional with the development of Radar Technology
Absorbing material such as ferrite, metal fine powder, carborundum, graphite, conductive fiber etc. are limited to that absorption band is narrow, density is big etc. and lacked
Point, can not realize effective protection to aircraft and pilot's safety.Therefore, exploitation has light weight, channel wide and inhaled
The New Radar Absorbing agent for receiving the feature such as strong has great importance.
CNT (CNTs) has excellent electrical property, and its huge draw ratio causes CNT to be easy in matrix
Middle formation conductive network, this causes the excess effusion value of CNT to be less than traditional carbon black and graphite wave absorbing agent, thus relatively low amount carbon
Nanotube is that can reach and high content graphite, carbon black identical electric conductivity.In addition, CNT also has, specific surface area is big, matter
Amount is light, high mechanical strength, it is corrosion-resistant the advantages of, thus CNT has the potentiality for preparing " light, thin, strong, width " absorbing material.
But pure nano-carbon tube, due to missing magnetic losses, impedance matching is poor, electromagnetic wave easily reflects in material surface, thus table
Reveal poor absorbing property, the application in ripple field is being inhaled this strongly limits CNT.In order to improve the resistance of CNT
Anti- matching, CNT is modified it is most important, the overwhelming majority report be conceived to it is miscellaneous with magnetic particle in CNT
Change.Such as Chen (Nanoscale, 2014,6,6440-6447) is proposed γ-Fe2O3Being packed into inside CNT can be by
Reflection loss is down to -32.7dB;And for example Li etc. (ACS Appl.Mater.Interfaces 2017,9,2973-2983) will
Fe3O4Nano particle, which is supported on carbon nano tube surface, to be down to -43dB by reflection loss.And the disadvantage of hydridization method is operation
It is cumbersome, finer structure control is often needed, in addition, magnetic particle and CNT adhesion are weaker and are easily stripped, and
Magnetic particle is easily oxidized, and these all strongly limit the utilization of hydridization method.
Direct fluorination technology is the effective means of carbon nano-tube modification, and its is simple to operate, cheap, and effect is notable, by
Greatly paid close attention to people.It can regulate and control electric conductivity, the dielectricity of CNT, thus fluorocarbons by controlling degree of fluorination
Nanotube has shown some superiority (J.Fluorine Chem.2009,130,1111-1116.) in electromagnetic shielding.But, Li
Et al. (Electrochimica Acta 107 (2013) 343-349) further result of study show directly fluorination carbon can be made to receive
The inner tube of mitron participates in fluorination reaction so that inner tube ordered structure is destroyed, and this causes the excellent electric conductivity funeral of CNT
Lose, that is, reduce the electromagnetic wave loss ability of inner tube.So as to study the absorbing property of the carbon fluoride nano-tube prepared at present not
It is good.Therefore, the integrality for inner tube structure being kept while CNT outer tube is fluorinated is to prepare the excellent many walls of absorbing property
The key of CNT (MWCNTs) wave absorbing agent.
The content of the invention
It is an object of the invention to provide a kind of preparation method of MWCNTs wave absorbing agents, its technique is simple, with low cost, profit
In industrialized production;Realize the outer tube of multi-walled carbon nanotube be fully fluorinated while can protection inner tube be not damaged
It is bad.
Another object of the present invention is to provide a kind of MWCNTs wave absorbing agents, it is fluorinated impedance matching layer outside CNT
Layer is formed by being directly fluorinated growth in situ, and structural stability is preferable, beneficial to the transmission of electromagnetic wave;The integrality of inner tube is good, electricity
Magnetic wave loss ability is excellent.
It is still another object of the present invention to provide a kind of MWCNTs absorbing materials, absorbing property is excellent, the addition of wave absorbing agent
Amount is few, and thickness of thin meets the requirement of novel wave-absorbing material " light, thin, strong, width ".
What embodiments of the invention were realized in:
A kind of preparation method of MWCNTs wave absorbing agents, it includes:The is carried out to multi-walled carbon nanotube at a temperature of 0-30 DEG C
Once it is fluorinated, then carrying out second to multi-walled carbon nanotube at a temperature of 100-190 DEG C is fluorinated.
A kind of MWCNTs wave absorbing agents, are made using above-mentioned preparation method.
A kind of MWCNTs absorbing materials, including resin material and above-mentioned wave absorbing agent.
The beneficial effect of the embodiment of the present invention is:
Many wall carbon are received by the preparation method for the MWCNTs wave absorbing agents that the present invention is provided at 0-30 DEG C close under conditions of room temperature
Mitron carries out first time fluorination, and its reaction condition is gentle, is only fluorinated the outer layer of multi-walled carbon nanotube, and second of fluorination exists
Reacted at a high temperature of 100-190 DEG C, degree of fluorination is more violent, the outer layer of multi-walled carbon nanotube is formed by abundant fluorination
Impedance matching layer.Fluorination for the first time is in outer layer formation fluorinated layer, and it can hinder fluorine gas to enter internal layer, prevents internal layer at second
It is fluorinated in fluorination, loss ability of the holding inner tube to electromagnetic wave.Impedance matching layer is in situ in outer layer by fluorination operation twice
Generation, Stability Analysis of Structures can effectively reduce reflection of the multi-walled carbon nanotube to electromagnetic wave.The above method is only needed to multi-wall carbon nano-tube
Pipe is fluorinated twice, and technique is simple, with low cost, is conducive to industrialized production.
The MWCNTs wave absorbing agents that the present invention is provided, are made by above-mentioned preparation method, and the wave absorbing agent is in similar to electric wire
Structure, its inner tube integrality is good, and positioned at the impedance matching layer Stability Analysis of Structures of outer layer, absorbing property is excellent.
The MWCNTs absorbing materials that the present invention is provided, including resin material and above-mentioned wave absorbing agent, the wave absorbing agent after fluorination
The dispersive property that absorbing property is good and it is in resin material is good, and the absorbing material mechanical performance and absorbing property are excellent.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be attached to what is used required in embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore is not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the high resolution TEM figure for the MWCNTs wave absorbing agents that the embodiment of the present invention 2 is provided;
The electromagnetic performance of reflection loss is surveyed when Fig. 2 is the MWCNTs absorbing material different-thickness of the offer of the embodiment of the present invention 2
Attempt;
The electromagnetic performance of reflection loss is surveyed when Fig. 3 is the MWCNTs absorbing material different-thickness of comparative example 1 of the present invention offer
Attempt.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
MWCNTs wave absorbing agents, its preparation method and the absorbing material of the embodiment of the present invention are specifically described below.
A kind of preparation method of MWCNTs wave absorbing agents, including:First is carried out to multi-walled carbon nanotube at a temperature of 0-30 DEG C
Secondary fluorination, then carries out second to multi-walled carbon nanotube at a temperature of 100-190 DEG C and is fluorinated.
Impedance matching layer is by fluorination operation twice in the outer layer in-situ preparation of multi-walled carbon nanotube, Stability Analysis of Structures.First
Secondary fluorination reaction mild condition, only the outer layer formation fluorinated layer in multi-walled carbon nanotube, it can hinder fluorine gas to enter internal layer, prevent
Internal layer is fluorinated in being fluorinated at second, maintains the integrality of internal layer.
In the present invention, fluorination for the first time and second of fluorination are former as fluorination using the fluorination mixed gas containing fluorine gas
Material is fluorinated.
Mixed gas is fluorinated in addition to containing fluorine gas, in addition to inert gas.It should be noted that inert gas is broad sense
On inert gas, such as but inert gas in the narrow sense as helium, neon, argon gas, Krypton, xenon, radon gas;Can also
It is the extremely low gas of the reactivities such as nitrogen, carbon dioxide;Can be any combination of above-mentioned various gases, i.e., comprising upper
State at least one of various gases.Inert gas is used for the concentration for diluting fluorine gas, controls the degree of fluorination reaction;While its
Property torpescence, it is to avoid and multi-walled carbon nanotube reacts.
In addition, above-mentioned fluorination mixed gas alternatively also includes oxygen, it, can be by while concentration of fluorine is diluted
Oxy radical is incorporated into CNT outer wall, increases the polarizable degree of carbon fluoride nano-tube.
It is preferred that inert gas selects at least one of helium or argon gas, it is easy to get, cost is relatively low.
Further, nitrogen displacement is carried out to reaction vessel before first time fluorination operation, its concrete operations is:To reaction
Nitrogen is filled with container, and gas in reaction vessel is drawn to.It is preferred that after extraction gas in container in reaction vessel
Pressure be less than 100Pa.The purpose of nitrogen displacement is to remove the indefinite vapor of composition and oxygen etc. in reaction vessel, prevents
Fluorination reaction is impacted;It is easy to control the concentration of fluorine gas simultaneously, improves the controllability of fluorination reaction.Further it is preferred that
The number of times of nitrogen displacement operation is at least twice, it is ensured that fully remove the foreign gas in reactor.In addition, the present invention is for the first time
The raw materials such as fluorination mixed gas, oxygen and the multi-walled carbon nanotube that fluorination and second of fluorination are added preferably first are dried again
Input reaction, it is ensured that fluorination effect.
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 carries out closed fluorination reaction completion.Specifically, after nitrogen displacement, fluorination mixed gas is passed through into reaction vessel to reaction
Pressure reaches 40-80KPa in container, and 1-3h is reacted at a temperature of 0-30 DEG C and completes to be fluorinated for the first time, it is in multi-walled carbon nanotube
Outer layer formation fluorinated layer and to internal layer carry out protective separation.Reaction vessel residual gas is removed, fluorine is passed through into reaction vessel
Change pressure in mixed gas to reaction vessel and reach 40-80KPa, 100-190 DEG C, reaction are warming up to 1-10 DEG C/min speed
1-3h completes second and is fluorinated, and forms impedance matching layer.
In above-mentioned fluorination operation, fluorination for the first time and the volume for being fluorinated fluorine gas in the fluorination mixed gas used for the second time
Fraction is preferably 5-20%, and the fluorination of its outer layer is abundant, impedance matching layer Stability Analysis of Structures.
In addition, the preparation of wave absorbing agent can also be that fluorinated materials are continually fed into reaction vessel to be fluorinated.Specifically,
After nitrogen displacement, fluorination mixed gas is continually fed into reaction vessel with 0.2-5L/min speed, at a temperature of 0-30 DEG C
1-3h is reacted to complete to be fluorinated for the first time;Continuation is continually fed into fluorination gaseous mixture into reaction vessel with 0.2-5L/min speed
Body, while being warming up to 100-190 DEG C with 1-10 DEG C/min speed, reaction 1-3h completes second and is fluorinated, and terminates ventilation.Preferably
Ground, in fluorination operation, the volume fraction of fluorine gas is 0.5-2% in fluorination mixed gas, and the fluorination of its outer layer is abundant, and internal layer is complete
Property is good.
The above-mentioned preparation method of wave absorbing agent, it is only necessary to be fluorinated twice to multi-walled carbon nanotube, technique is simple, and cost is low
It is honest and clean, be conducive to industrialized production.
Using MWCNTs wave absorbing agents made from above-mentioned preparation method, lining integrity is good, the impedance matching Rotating fields of outer layer
Stable, the absorbing property of wave absorbing agent is excellent.
A kind of MWCNTs absorbing materials, including resin material and above-mentioned wave absorbing agent.Wave absorbing agent disperses in resin material
Uniformly, the mechanical performance of absorbing material is excellent, and absorbing property is uniform, notable.
It is preferred that the one kind of resin material in paraffin or epoxy resin, absorbing material is disperseed by above-mentioned wave absorbing agent
It is made in such as paraffin and epoxy resin Polymer material.
When resin material is paraffin, wave absorbing agent and paraffin mixing.The mass ratio of wave absorbing agent and paraffin is preferably 0.05-
0.15∶1.During preparation, equal phase dispersant liquid is formed in the chloroformic solution that wave absorbing agent is scattered in paraffin, is removed using methods such as revolvings
Chloroform.
When resin material is epoxy resin, wave absorbing agent and epoxy resin mixing.The mass ratio of wave absorbing agent and epoxy resin
Preferably 0.02-0.05: 1.Further preferably epoxy resin be selected from bisphenol F epoxy resin, bisphenol A-type E51 epoxy resin,
At least one of bisphenol A-type E44 epoxy resin, bisphenol A-type E42 epoxy resin and bisphenol A-type E54 epoxy resin.
Further, when resin material is epoxy resin, absorbing material also includes curing agent, for being consolidated to material
Change.
It is preferred that curing agent be selected from Diamines curing agent such as polyetheramine D230,4,4 '-MDA (DDM), or
One kind in person's acid anhydride type curing agent such as phthalic anhydride, tetrabydrophthalic anhydride.The quality of curing agent and epoxy resin
Than for 1: 2-4.Its solidification effect of aforesaid operations condition is good, the good mechanical performance of absorbing material.
During preparation, equal phase dispersant liquid is formed in the acetone soln that wave absorbing agent is scattered in epoxy resin, using the side such as revolving
Method removes acetone.Curing agent vacuum abjection bubble is added, 3- is reacted at 120-180 DEG C after 60 DEG C of -80 DEG C of reaction 1-3h successively
5h completes heat stepwise solidification.
Above-mentioned absorbing material, wave absorbing agent absorbing property is good, and wave absorbing agent addition is small, the wave absorbing agent good dispersion after fluorination,
The mechanicalness of absorbing material is good, and molding thickness is small, and absorbing material meets the requirement of novel wave-absorbing material " light, thin, strong, width ".
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 40KPa for pressure in 5% fluorine gas and mixed gas to the reactor of nitrogen, in 25 DEG C of temperature
The lower insulation 3h of degree.Extraction kettle residual gas, the mixed of fluorine gas that fluorine gas volume fraction is 5% and nitrogen is passed through into reactor
Close gas to reactor in pressure reach 40KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 1h, must inhale
Ripple agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, rotated
Chloroform is removed, absorbing material is obtained.
Embodiment 2
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reactor
Inside it is passed through fluorine gas volume fraction and reaches 60KPa for pressure in 5% fluorine gas and mixed gas to the reactor of nitrogen, in 25 DEG C of temperature
Lower insulation 2h.Extraction kettle residual gas, the mixing of fluorine gas and nitrogen that fluorine gas volume fraction is 5% is passed through into reactor
In gas to reactor pressure reach 60KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 1h, obtain suction ripple
Agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, revolving is removed
Chloroform is removed, absorbing material is obtained.
Embodiment 3
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 80KPa for pressure in 5% fluorine gas and mixed gas to the reactor of nitrogen, in 25 DEG C of temperature
The lower insulation 1h of degree.Extraction kettle residual gas, the mixed of fluorine gas that fluorine gas volume fraction is 5% and nitrogen is passed through into reactor
Close gas to reactor in pressure reach 80KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 1h, must inhale
Ripple agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, rotated
Chloroform is removed, absorbing material is obtained.
Embodiment 4
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
The fluorine gas that fluorine gas volume fraction is 5% is passed through in kettle and reaches 60KPa with pressure in nitrogen mixed gas to reactor, in 5 DEG C of temperature
Lower insulation 1h.Extraction kettle residual gas, the mixed of fluorine gas that fluorine gas volume fraction is 5% and nitrogen is passed through into reactor
Close gas to reactor in pressure reach 60KPa, immediately with 5 DEG C/min speed by gas heating to 150 DEG C, be incubated 1h, must inhale
Ripple agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, rotated
Chloroform is removed, absorbing material is obtained.
Embodiment 5
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 5% fluorine gas and mixed gas to the reactor of argon gas, in 30 DEG C of temperature
The lower insulation 1h of degree.Extraction kettle residual gas, the mixed of fluorine gas that fluorine gas volume fraction is 5% and argon gas is passed through into reactor
Close gas to reactor in pressure reach 60KPa, immediately with 5 DEG C/min speed by gas heating to 190 DEG C, be incubated 1h, must inhale
Ripple agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, rotated
Chloroform is removed, absorbing material is obtained.
Embodiment 6
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 5% fluorine gas and mixed gas to the reactor of helium, in 15 DEG C of temperature
The lower insulation 1h of degree.Extraction kettle residual gas, the mixed of fluorine gas that fluorine gas volume fraction is 5% and helium is passed through into reactor
Close gas to reactor in pressure reach 60KPa, immediately with 10 DEG C/min speed by gas heating to 190 DEG C, be incubated 1h, obtain
Wave absorbing agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, revolved
Chloroform is evaporated off, absorbing material is obtained.
Embodiment 7
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 10% fluorine gas and mixed gas to the reactor of nitrogen, at 20 DEG C
At a temperature of be incubated 1h.Extraction kettle residual gas, pressure is passed through in oxygen to reactor into reactor and reaches 20KPa, to anti-
Answer kettle to be passed through fluorine gas volume fraction and reach 60KPa for pressure in 10% fluorine gas and mixed gas to the reactor of nitrogen, immediately with 5
DEG C/gas heating to 100 DEG C, is incubated 1h, obtains wave absorbing agent by min speed.By 100mg wave absorbing agents ultrasonic disperse in containing
Uniform dispersion is formed in paraffin/chloroformic solution of 1000mg paraffin, revolving removes chloroform, obtains absorbing material.
Embodiment 8
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 5% fluorine gas and mixed gas to the reactor of nitrogen, in 25 DEG C of temperature
The lower insulation 1h of degree.Extraction kettle residual gas, the mixed of fluorine gas that fluorine gas volume fraction is 5% and nitrogen is passed through into reactor
Close gas to reactor in pressure reach 60KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 3h, must inhale
Ripple agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, rotated
Chloroform is removed, absorbing material is obtained.
Embodiment 9
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 5% fluorine gas and mixed gas to the reactor of nitrogen, in 25 DEG C of temperature
The lower insulation 1h of degree.Extraction kettle residual gas, the mixed of fluorine gas that fluorine gas volume fraction is 5% and nitrogen is passed through into reactor
Close gas to reactor in pressure reach 60KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 1h, must inhale
Ripple agent.50mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, revolving is removed
Chloroform is removed, absorbing material is obtained.
Embodiment 10
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 5% fluorine gas and mixed gas to the reactor of nitrogen, in 25 DEG C of temperature
The lower insulation 1h of degree.Extraction kettle residual gas, the mixed of fluorine gas that fluorine gas volume fraction is 5% and nitrogen is passed through into reactor
Close gas to reactor in pressure reach 60KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 1h, must inhale
Ripple agent.150mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, rotated
Chloroform is removed, absorbing material is obtained.
Embodiment 11
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 10% fluorine gas and mixed gas to the reactor of nitrogen, at 20 DEG C
At a temperature of be incubated 1h.Extraction kettle residual gas, fluorine gas and nitrogen that fluorine gas volume fraction is 10% are passed through into reactor
Mixed gas to reactor in pressure reach 60KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 1h,
Obtain wave absorbing agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg,
Revolving removes chloroform, obtains absorbing material.
Embodiment 12
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 20% fluorine gas and mixed gas to the reactor of nitrogen, at 25 DEG C
At a temperature of be incubated 1h.Extraction kettle residual gas, fluorine gas and nitrogen that fluorine gas volume fraction is 20% are passed through into reactor
Mixed gas to reactor in pressure reach 60KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 1h,
Obtain wave absorbing agent.100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg,
Revolving removes chloroform, obtains absorbing material.
Embodiment 13
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.With 1L/
Min speed is continually fed into the mixed gas of the fluorine gas that fluorine gas volume fraction is 1% and nitrogen into reactor, in 25 DEG C of temperature
Lower insulation 1h;Continue to be continually fed into fluorine gas and nitrogen of the fluorine gas volume fraction as 1% into reactor using 1L/min speed
Mixed gas, while with 2 DEG C/min speed by gas heating to 100 DEG C, being incubated 1h, terminates ventilation, obtains wave absorbing agent.Will
100mg wave absorbing agents ultrasonic disperse forms uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, and revolving removes dechlorination
It is imitative, obtain absorbing material.
Embodiment 14
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.With 1L/
Min speed is continually fed into the mixed gas of the fluorine gas that fluorine gas volume fraction is 1% and nitrogen into reactor, in 25 DEG C of temperature
Lower insulation 1h;Continue to be continually fed into fluorine gas and nitrogen of the fluorine gas volume fraction as 1% into reactor using 1L/min speed
Mixed gas, while with 2 DEG C/min speed by gas heating to 150 DEG C, being incubated 1h, stops ventilation, obtains wave absorbing agent.Will
100mg wave absorbing agents ultrasonic disperse forms uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, and revolving removes dechlorination
It is imitative, obtain absorbing material.
Embodiment 15
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.With 1L/
Min speed is continually fed into the mixed gas of the fluorine gas that fluorine gas volume fraction is 1% and nitrogen into reactor, in 25 DEG C of temperature
Lower insulation 1h;Continue to be continually fed into fluorine gas and nitrogen of the fluorine gas volume fraction as 1% into reactor using 1L/min speed
Mixed gas, while with 2 DEG C/min speed by gas heating to 190 DEG C, being incubated 1h, terminates ventilation, obtains wave absorbing agent.Will
100mg wave absorbing agents ultrasonic disperse forms uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, and revolving removes dechlorination
It is imitative, obtain absorbing material.
Embodiment 16
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.With 0.2L/
Min speed is continually fed into the mixed gas of the fluorine gas that fluorine gas volume fraction is 2% and nitrogen into reactor, in 25 DEG C of temperature
Lower insulation 1h;Continuation is continually fed into fluorine gas volume fraction into reactor as 2% fluorine gas and nitrogen using 0.2L/min speed
Mixed gas, while with 2 DEG C/min speed by gas heating to 150 DEG C, be incubated 1h, terminate ventilation, obtain wave absorbing agent.Will
100mg wave absorbing agents ultrasonic disperse forms uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, and revolving removes dechlorination
It is imitative, obtain absorbing material.
Embodiment 17
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.With 2L/
Min speed is continually fed into the mixed gas of the fluorine gas that fluorine gas volume fraction is 0.5% and nitrogen into reactor, in 25 DEG C of temperature
The lower insulation 1h of degree;Continuation is continually fed into fluorine gas volume fraction into reactor as 0.5% fluorine gas and nitrogen using 2L/min speed
The mixed gas of gas, while with 2 DEG C/min speed by gas heating to 150 DEG C, being incubated 1h, stops ventilation, obtains wave absorbing agent.
100mg wave absorbing agents ultrasonic disperse is formed into uniform dispersion in paraffin/chloroformic solution of the paraffin containing 1000mg, revolving removes dechlorination
It is imitative, obtain absorbing material.
Embodiment 18
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 10% fluorine gas and mixed gas to the reactor of nitrogen, at 25 DEG C
At a temperature of be incubated 1h.Extraction kettle residual gas, fluorine gas and nitrogen that fluorine gas volume fraction is 10% are passed through into reactor
Mixed gas to reactor in pressure reach 60KPa, immediately with 2 DEG C/min speed by gas heating to 190 DEG C, be incubated 1h,
Obtain wave absorbing agent.By 150mg wave absorbing agents ultrasonic disperse in epoxy resin/acetone soln of the E51 epoxy resin of bisphenol A-type containing 3000mg
After middle formation uniform dispersion, revolving removing acetone, addition 1000mg curing agent D230, froth in vacuum successively at a temperature of 80 DEG C
It is incubated 2h and 3h is incubated at a temperature of 120 DEG C and complete solidification, obtains absorbing material.
Embodiment 19
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.To reaction
Fluorine gas volume fraction is passed through in kettle and reaches 60KPa for pressure in 10% fluorine gas and mixed gas to the reactor of nitrogen, at 25 DEG C
At a temperature of be incubated 1h.Extraction kettle residual gas, fluorine gas and nitrogen that fluorine gas volume fraction is 10% are passed through into reactor
Mixed gas to reactor in pressure reach 60KPa, immediately with 2 DEG C/min speed by gas heating to 190 DEG C, be incubated 1h,
Obtain wave absorbing agent.By 150mg wave absorbing agents ultrasonic disperse in epoxy resin/acetone soln of the E51 epoxy resin of bisphenol A-type containing 3000mg
Middle formation uniform dispersion, revolving removes acetone, adds after 750mg curing agent DDM, froth in vacuum and is protected successively at a temperature of 80 DEG C
Warm 2h is simultaneously incubated 4h completion solidifications at a temperature of 150 DEG C, obtains absorbing material.
Comparative example 1
A kind of absorbing material, is made by following methods:The MWCNTs ultrasonic disperses that 100mg is dried are in paraffin containing 1000mg
Paraffin/chloroformic solution in form uniform dispersion, revolving removes chloroform, obtains absorbing material.
Comparative example 2
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.At 25 DEG C
At a temperature of be passed through into reactor fluorine gas volume fraction be 5% fluorine gas and nitrogen mixed gas to reactor in pressure reach
60KPa, immediately with 5 DEG C/min speed by gas heating to 100 DEG C, be incubated 1h, obtain wave absorbing agent.By 100mg wave absorbing agents ultrasound
Uniform dispersion is formed in the paraffin/chloroformic solution for being scattered in the paraffin containing 1000mg, revolving removes chloroform, obtains absorbing material.
Comparative example 3
A kind of absorbing material, is made by following methods:The 500mg MWCNTs dried are inserted in fluorination reaction kettle, to anti-
Answer and pressure in nitrogen and gas bleeding to reactor is passed through in kettle is less than 100Pa, complete three above-mentioned nitrogen displacements.At 25 DEG C
At a temperature of be passed through into reactor fluorine gas volume fraction be 10% fluorine gas and nitrogen mixed gas to reactor in pressure reach
60KPa, immediately with 5 DEG C/min speed by gas heating to 190 DEG C, be incubated 1h, obtain wave absorbing agent.By 100mg wave absorbing agents ultrasound
Uniform dispersion is formed in the paraffin/chloroformic solution for being scattered in the paraffin containing 1000mg, revolving removes chloroform, obtains absorbing material.
The embodiment 1-19 and comparative example 1-3 absorbing materials provided are pressed into external diameter 7mm, internal diameter 3mm concentric circles
Ring simultaneously carries out electromagnetic performance test, the test thickness of each optimal absorbing property of absorbing material and corresponding reflection loss performance such as table
Shown in 1.
The absorbing material electromagnetic performance of table 1. tests table
The absorbing material of comparative example 1 is scattered in paraffin using original multi-walled carbon nanotube and is made, comparative example 2 and comparative example 3
The absorbing material of offer is once directly fluorinated obtained under the high temperature conditions to multi-walled carbon nanotube.As shown in Table 1, implement
The magnetic particles for the absorbing material that example 1-19 is provided are excellent, and it is substantially better than the suction of the absorbing material of comparative example 1-3 propositions
Ripple performance.
To embodiment 2 provide MWCNTs wave absorbing agents carry out high resolution TEM scanning, its result as shown in figure 1,
The outer layer of multi-walled carbon nanotube is obscured, and inner layer tube wall is parallel with pipe axle, and tube wall is high-visible, MWCNTs wave absorbing agents it is above-mentioned similar
Show that fluorination only occurs in outermost layer in the structure of electric wire, internal layer is not fluorinated.
Reflection loss performance of the MWCNTs absorbing materials that embodiment 2 is provided in different-thickness is as shown in Fig. 2 its thickness
Significantly, optimal reflection loss reaches -69dB to absorbing property during for 1.5mm.Comparative example 1 is using the absorbing material provided in difference
Reflection loss performance during thickness is as shown in figure 3, wave absorbing agent is all higher than -10dB, suction ripple when thickness is less than 3mm in reflection loss
Poor performance.
In summary, the preparation method of the MWCNTs wave absorbing agents of the embodiment of the present invention, it is only necessary to carried out to multi-walled carbon nanotube
It is fluorinated twice, technique is simple, with low cost, is conducive to industrialized production;Fluorination for the first time is in outer layer formation impedance layer is prevented
Layer is fluorinated, second fluorination realize outer tube is fully fluorinated while can protection inner tube do not damaged by fluorination.It is made
MWCNTs wave absorbing agents, fluorination impedance matching layer is directly fluorinated growth in situ in CNT outer layer and forms, stability and scattered
Property is preferable;The integrality of inner tube is good, and absorbing property is excellent.Using MWCNTs absorbing materials made from the MWCNTs wave absorbing agents, inhale
Ripple excellent performance, the addition of wave absorbing agent is few, and the wave absorbing agent good dispersion after fluorination, the mechanicalness of absorbing material is good, and shaping is thick
Degree is small, meets the requirement of novel wave-absorbing material " light, thin, strong, width ".
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of MWCNTs wave absorbing agents, it is characterised in that including:To multi-walled carbon nanotube at a temperature of 0-30 DEG C
First time fluorination is carried out, then carrying out second to the multi-walled carbon nanotube at a temperature of 100-190 DEG C is fluorinated.
2. preparation method according to claim 1, it is characterised in that the first time fluorination and second of fluorination are equal
The multi-walled carbon nanotube is fluorinated using fluorination mixed gas, the fluorination mixed gas includes inert gas and fluorine
Gas;Alternatively, the fluorination mixed gas also includes oxygen.
3. preparation method according to claim 2, it is characterised in that be also included in before the first time fluorination to reaction
Container carries out nitrogen displacement;Preferably, pressure is less than 100Pa in the reaction vessel after nitrogen displacement;It is further preferred that nitrogen
The number of times of gas displacement is at least twice.
4. preparation method according to claim 3, it is characterised in that after nitrogen displacement, is passed through into the reaction vessel
The fluorination mixed gas to pressure is 40-80KPa, and 1-3h is reacted at a temperature of 0-30 DEG C and completes the first time fluorination, is removed
The residual gas gone in the reaction vessel, it is 40- to be passed through the fluorination mixed gas to pressure to the reaction vessel
80KPa, is warming up to 100-190 DEG C, reaction 1-3h completes described second and is fluorinated with 1-10 DEG C/min speed;Preferably, institute
The volume fraction for stating fluorine gas described in fluorination mixed gas is 5-20%.
5. preparation method according to claim 3, it is characterised in that after nitrogen displacement, with 0.2-5L/min speed to
The fluorination mixed gas is continually fed into the reaction vessel, 1-3h is reacted at a temperature of 0-30 DEG C and completes the first time fluorine
Change, continuation the fluorination mixed gas is continually fed into the reaction vessel with 0.2-5L/min speed, with 1-10 DEG C/
Min speed is warming up to 100-190 DEG C, and insulation 1-3h completes described second and is fluorinated;Preferably, in the fluorination mixed gas
The volume fraction of the fluorine gas is 0.5-2%.
6. a kind of MWCNTs wave absorbing agents, it is characterised in that be made as the preparation method described in claim any one of 1-5.
7. a kind of MWCNTs absorbing materials, it is characterised in that including the wave absorbing agent described in resin material and claim 6.
8. absorbing material according to claim 7, it is characterised in that the resin material is paraffin;Preferably, it is described to inhale
The mass ratio of ripple agent and the paraffin is 0.05-0.15: 1.
9. absorbing material according to claim 7, it is characterised in that the resin material is epoxy resin;Preferably, institute
The mass ratio for stating wave absorbing agent and the epoxy resin is 0.02-0.05: 1;Preferably, the epoxy resin is selected from Bisphenol F epoxy
Resin, bisphenol A-type E51 epoxy resin, bisphenol A-type E44 epoxy resin, bisphenol A-type E42 epoxy resin and bisphenol A-type E54 rings
At least one of oxygen tree fat.
10. absorbing material according to claim 9, it is characterised in that also including curing agent;Preferably, the curing agent
Mass ratio with the epoxy resin is 1: 2-4;Preferably, the curing agent is selected from Diamines curing agent and acid anhydride type curing agent
In one kind;Preferably, the curing agent is selected from polyetheramine D230,4,4 '-MDA (DDM), phthalic acid
One kind in acid anhydride, tetrabydrophthalic anhydride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710442184.0A CN107163912B (en) | 2017-06-13 | 2017-06-13 | A kind of MWCNTSWave absorbing agent, preparation method and absorbing material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710442184.0A CN107163912B (en) | 2017-06-13 | 2017-06-13 | A kind of MWCNTSWave absorbing agent, preparation method and absorbing material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107163912A true CN107163912A (en) | 2017-09-15 |
CN107163912B CN107163912B (en) | 2019-08-20 |
Family
ID=59825660
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710442184.0A Active CN107163912B (en) | 2017-06-13 | 2017-06-13 | A kind of MWCNTSWave absorbing agent, preparation method and absorbing material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107163912B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108682527A (en) * | 2018-05-10 | 2018-10-19 | 四川大学 | Magnetic fluorinated carbon material wave absorbing agent, preparation method, application and absorbing 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 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102730664A (en) * | 2012-07-04 | 2012-10-17 | 四川大学 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
CN103276593A (en) * | 2013-05-28 | 2013-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for enhancing carbon nano tube fiber by utilizing fluorine-removing cross-linking reaction |
-
2017
- 2017-06-13 CN CN201710442184.0A patent/CN107163912B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102730664A (en) * | 2012-07-04 | 2012-10-17 | 四川大学 | Carbon nano-tube with fluorine-containing surface and preparation method thereof |
CN103276593A (en) * | 2013-05-28 | 2013-09-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for enhancing carbon nano tube fiber by utilizing fluorine-removing cross-linking reaction |
Non-Patent Citations (2)
Title |
---|
JEONG-MINLEE,等: "A high resolution XPS study of sidewall functionalized MWCNTs by fluorination", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
JI SUN IM,等: "Fluorination effects of MWCNT additives for EMI shielding efficiency by developed conductive network in epoxy complex", 《JOURNAL OF FLUORINE CHEMISTRY》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108682527A (en) * | 2018-05-10 | 2018-10-19 | 四川大学 | Magnetic fluorinated carbon material wave absorbing agent, preparation method, application and absorbing 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 |
Also Published As
Publication number | Publication date |
---|---|
CN107163912B (en) | 2019-08-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | A generalizable strategy for constructing ultralight three-dimensional hierarchical network heterostructure as high-efficient microwave absorber | |
Zhu et al. | Ultralight, compressible, and anisotropic MXene@ Wood nanocomposite aerogel with excellent electromagnetic wave shielding and absorbing properties at different directions | |
Song et al. | Alignment of graphene sheets in wax composites for electromagnetic interference shielding improvement | |
Yang et al. | Research progress on carbon-based materials for electromagnetic wave absorption and the related mechanisms | |
CN103367726B (en) | Si-C composite material and preparation method thereof, lithium ion battery | |
Lyu et al. | High-performance microwave absorption of MOF‐derived Co3O4@ N-doped carbon anchored on carbon foam | |
Meng et al. | Graphene oxide-assisted Co-sintering synthesis of carbon nanotubes with enhanced electromagnetic wave absorption performance | |
Liu et al. | Excellent microwave absorbing property of multiwalled carbon nanotubes with skin–core heterostructure formed by outer dominated fluorination | |
CN103333465B (en) | Preparation method of FeCo@MWNTs/epoxy resin based wave absorbing composite material | |
CN112047386A (en) | Heating modified MXene/ferroferric oxide composite wave-absorbing material and preparation method thereof | |
CN107163912B (en) | A kind of MWCNTSWave absorbing agent, preparation method and absorbing material | |
CN106898881A (en) | A kind of three-dimensional orientation silicon carbide nanometer line/carbon inhales the preparation method of ripple aeroge | |
Ding et al. | Heterogeneous network constructed by high aspect-ratio Kapok biomass microtube for lightweight and broadband microwave absorbent | |
CN104673185A (en) | Method for preparing reduced graphene oxide/CoFe2O4/Ag composite wave-absorbing material | |
CN108682527A (en) | Magnetic fluorinated carbon material wave absorbing agent, preparation method, application and absorbing material | |
CN107934945A (en) | A kind of method for preparing magnetic graphene using molysite gas phase intercalation and microwave technology | |
Wang et al. | Architecture-inspired N-doped carbon nanotube bridging well-arranged MXene nanosheets toward efficient electromagnetic wave absorption | |
Zhou et al. | A freestanding 3D heterophase tungsten disulfide-based aerogel as an ultrathin microwave absorber in the Ku-band | |
CN105244477A (en) | Silicon carbon composite negative electrode material and preparation method therefor | |
Ye et al. | Microwave absorption properties of Ni/C@ SiC composites prepared by precursor impregnation and pyrolysis processes | |
CN109294518A (en) | A kind of graphene aerogel/SiO of core-shell structure2Wave-absorbing material applied to buildings and preparation method | |
Shu et al. | Polyaniline-based networks combined with Fe3O4 hollow spheres and carbon balls for excellent electromagnetic wave absorption | |
Rong et al. | Carbonized fibers with multi-elemental doping and hollow architecture derived from natural cotton for tunable microwave absorption properties | |
CN105590756B (en) | A kind of preparation method of micro/nano-scale graphene/lithium titanate composite anode material | |
Chen et al. | Porous CoO/carbon foam composites synthesized by solvothermal method for supercapacitor and enhanced microwave absorption applications |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |