CN110177449A - A kind of carbon nanotube base Electromagnetic heating absorbing material and its preparation method and application - Google Patents
A kind of carbon nanotube base Electromagnetic heating absorbing material and its preparation method and application Download PDFInfo
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- CN110177449A CN110177449A CN201910413893.5A CN201910413893A CN110177449A CN 110177449 A CN110177449 A CN 110177449A CN 201910413893 A CN201910413893 A CN 201910413893A CN 110177449 A CN110177449 A CN 110177449A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 80
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000010438 heat treatment Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000011358 absorbing material Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 68
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 carbon nano tube compound Chemical class 0.000 claims abstract description 28
- 239000002077 nanosphere Substances 0.000 claims abstract description 19
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002131 composite material Substances 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000008246 gaseous mixture Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000010792 warming Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910017488 Cu K Inorganic materials 0.000 description 3
- 229910017541 Cu-K Inorganic materials 0.000 description 3
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 1
- 229910003962 NiZn Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention discloses a kind of carbon nanotube base Electromagnetic heating absorbing materials and its preparation method and application, belong to field of functional materials.The preparation method of the carbon nanotube base Electromagnetic heating absorbing material, comprising the following steps: 1) FeO (OH)/carbon nano tube compound material preparation；2)Fe3O4The preparation of@Fe core-shell nanospheres/carbon nano tube compound material.Using carbon nanotube as matrix in the present invention, nano material is generated on carbon nanotube matrix by in-situ chemical reaction, to obtain carbon nanotube base Electromagnetic heating absorbing material, preparation method of the invention is stable, controllable, simple to operation, and prepared Electromagnetic heating absorbing material has excellent electro-magnetic wave absorption ability.
Description
Technical field
The invention belongs to field of functional materials, and in particular to a kind of carbon nanotube base Electromagnetic heating absorbing material and its preparation
Method and purposes.
Background technique
In recent years, the development of Radar Technology, electronic equipment, wireless communication technology field high speed, thus bring day
Electromagnetic radiation pollution often in life is more and more common.This can not only interfere the normal operation of electromagnetic equipment, exist to electromagnetic equipment
The application of military field brings problem, while also threaten the health of the mankind.In order to solve the problems, such as that these are serious, in the past,
People have been working hard the electro-magnetic wave absorption for developing that efficient absorbability is strong, absorption band width is big, lightweight, matching thickness are thin
Material.In general, according to electromagnetic wave loss characteristic, electromagnetic wave absorbent material is classified as dielectric loss type material and magnetic loss type
Material two major classes.Common such as carbon material, magnetic metal and Ferrite Material is all widely used in manufacturing electro-magnetic wave absorption
Material.
Carbon nanotube (CNT) material can be regarded as winding the seamless hollow tubulose carbon material formed by graphite flake.Carbon is received
Mitron has a variety of excellent performances as a kind of important one-dimensional carbon nano material, inhales it in energy storage, catalysis and electromagnetic wave
The numerous areas such as receipts achieve huge progress.Especially because it has the characteristics that semiconductor property and high-strength light, at
For one of the important candidate of raw material of electro-magnetic wave absorption device.Although the carbon materials such as carbon nanotube have the small quality of density
Gently, the advantages that broad absorption band is wide, but its relatively high complex dielectric permittivity and poor magnetic conductivity lead to impedance mismatching seriously
Carbon material is limited in the extensive use in electro-magnetic wave absorption field；Fe simultaneously3O4Absorption band width, the thickness of equal magnetic materials is big,
The big equal various problems of density limit magnetic material in the practical application in electro-magnetic wave absorption field.And for single dielectric material
For material or magnetic material, excellent impedance matching is difficult to realize to obtain high electromagnetic wave absorption performance.So by setting
The composite material for counting magnetic material and dielectric material, is a kind of effective solution above problem using synergistic effect between the two
Method.Such as CoFe2O4It is compound with carbon nanotube, Fe3O4It is compound with graphene, NiZn ferrite and graphene are compound etc..Though
So compound by magnetic material and carbon material, electromagnetic wave absorption performance has substantive raising.However, how by simple
There are still certain difficulty to prepare high performance electromagnetic wave absorbent material for preparation method.
A kind of Electromagnetic heating absorbing material opening for absorbing material that be simple, haveing excellent performance is prepared in conclusion developing
Hair is of great significance with production.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of carbon nanotube base Electromagnetic heatings
Absorbing material and its preparation method and application, overcome the absorbing material in the presence of the prior art be difficult to meet strong absorbability,
The technological deficiency of the requirements such as broad absorption band, lightweight, thin matching thickness.
To achieve the goals above or other purposes, the present invention is achieved by the following technical solutions.
A kind of preparation method of carbon nanotube base Electromagnetic heating absorbing material, comprising the following steps:
1) FeO (OH)/carbon nano tube compound material preparation: ferric nitrate, carbon nanotube are added to ethyl alcohol and water by a.
In the mixed solvent, stirring；
B. acquired solution in the step a is heated, carries out processing after reaction and obtains FeO (the OH)/carbon
Nanometer tube composite materials；
2)Fe3O4@Fe core-shell nanospheres/carbon nano tube compound material preparation: will be obtained described in the step 1)
FeO (OH)/carbon nano tube compound material is heat-treated under hydrogen or hydrogen and argon gas mixed-gas environment, is cooled to room
Temperature is to get the Fe3O4@Fe core-shell nanospheres/carbon nano tube compound material.
Further, ferric nitrate in the step 1), carbon nanotube, water, ethyl alcohol mass ratio be 1:(0.01~0.04):
(30~35): (8~10).
Further, heating reaction temperature is 40~80 DEG C in the step 1), and the reaction time is 30~240min.
Preferably, it is cooled to room temperature, is centrifuged after reaction, gained precipitating is washed, dry to get the FeO
(OH)/carbon nano tube compound material.
Preferably, deionized water is respectively adopted in gained precipitating, ethyl alcohol is cleaned.It is highly preferred that using deionized water respectively
Three times with ethyl alcohol cleaning.
Preferably, drying condition is 60 DEG C of vacuum drying 12h.
Further, the temperature being heat-treated in the step 2) is 400~500 DEG C, and soaking time is 60~150min, is risen
Warm rate is 5~10 DEG C/min.
The present invention also provides using Fe prepared by above-mentioned preparation method3O4@Fe core-shell nanospheres/carbon nanotube is compound
Material.
The present invention also provides the carbon nanotube base Electromagnetic heating absorbing materials prepared by the above method in electro-magnetic wave absorption
The purposes of Material Field.
Second aspect of the present invention provides a kind of preparation method of carbon nanotube base Electromagnetic heating absorbing material, including following
Step:
1) FeO (OH)/carbon nano tube compound material preparation: ferric nitrate, carbon nanotube are added to ethyl alcohol and water by a.
In the mixed solvent, stirring；
B. acquired solution in step a is heated, carries out processing after reaction and obtains FeO (the OH)/carbon nanometer
Pipe composite material；
2)Fe2O3Hollow nano-sphere/carbon nano tube compound material preparation: by the gained FeO in the step (1)
(OH)/carbon nano tube compound material is heat-treated in hydrogen and argon gas gaseous mixture, and after treatment is distinguished in air or oxygen
It carries out heat treatment for the first time and second is heat-treated, be cooled to room temperature to get Fe2O3Hollow nano-sphere/carbon nanotube composite
Material.
Preferably, ferric nitrate in the step 1), carbon nanotube, water, ethyl alcohol mass ratio be 1:(0.01~0.04):
(30~35): (8~10).
Preferably, heating reaction temperature is 40~80 DEG C in the step 1), and the reaction time is 30~240min.
Preferably, it is cooled to room temperature, is centrifuged after reaction, gained precipitating is washed, dry to get the FeO
(OH)/carbon nano tube compound material.
Preferably, deionized water is respectively adopted in gained precipitating, ethyl alcohol is cleaned.It is highly preferred that using deionized water respectively
Three times with ethyl alcohol cleaning.
Preferably, drying condition is 60 DEG C of vacuum drying 12h.
Preferably, 400~450 DEG C of the heat treatment temperature in step 2) in hydrogen and argon gas gaseous mixture, soaking time: 90
~150min, heating rate: 1~10 DEG C/min.
Preferably, the heat treatment temperature of the first time heat treatment carried out in air or oxygen in step 2): 150~200
DEG C, soaking time: 90~180min, heating rate: 1~10 DEG C/min.
Preferably, the heat treatment temperature of second of the heat treatment carried out in air or oxygen in step 2): 200~300
DEG C, soaking time: 60~120min, heating rate: 1~10 DEG C/min.
By carrying out secondary heat treatment in air or oxygen in the present invention, heat treatment is by outer oxide at oxidation for the first time
Iron simultaneously forms part hollow structure, and second of heat treatment guarantees the complete formation of hollow structure, to obtain Fe2O3Hollow Nano
Ball/carbon nano tube compound material.
The present invention also provides using Fe prepared by above-mentioned preparation method2O3Hollow nano-sphere/carbon nanotube composite
Material.
The present invention also provides the carbon nanotube base Electromagnetic heating absorbing materials prepared by the above method in electro-magnetic wave absorption
The purposes of Material Field.
Using carbon nanotube as matrix in the present invention, nanometer is generated on carbon nanotube matrix by in-situ chemical reaction
Material, to obtain carbon nanotube base Electromagnetic heating absorbing material.It is stable using preparation method of the invention, controllable, simple easy
Operation, prepared Electromagnetic heating absorbing material have excellent electro-magnetic wave absorption ability.
Detailed description of the invention
Fig. 1 is the XRD diagram of composite wave-suction material obtained by embodiment 1 to embodiment 3；
Fig. 2 is the TEM figure of composite wave-suction material obtained by embodiment 1；
Fig. 3 is the TEM figure of composite wave-suction material obtained by embodiment 2；
Fig. 4 is the TEM figure of composite wave-suction material obtained by embodiment 3；
Fig. 5 is the XPS figure of composite wave-suction material obtained by embodiment 1；
Fig. 6 is the XPS figure of composite wave-suction material obtained by embodiment 2；
Fig. 7 is the XPS figure of composite wave-suction material obtained by embodiment 3；
Fig. 8 is the specific surface area of composite wave-suction material obtained by embodiment 1 to embodiment 3；
Fig. 9 is the absorbing property of composite wave-suction material obtained by embodiment 1；
Figure 10 is the absorbing property of composite wave-suction material obtained by embodiment 2；
Figure 11 is the absorbing property of composite wave-suction material obtained by embodiment 3.
Specific embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, those skilled in the art can be by this explanation
Other advantages and efficacy of the present invention can be easily understood for content disclosed by book.The present invention can also be by addition different specific
Embodiment is embodied or practiced, and the various details in this specification can also not carried on the back based on different viewpoints and application
From carrying out various modifications or alterations under spirit of the invention.
It should be noted that in the absence of conflict, the feature in following embodiment and embodiment can be combined with each other.Also
It should be appreciated that term used in the embodiment of the present invention is in order to describe specific specific embodiment, rather than in order to limit
Protection scope of the present invention.The test method of actual conditions is not specified in the following example, usually according to normal condition, or presses
According to condition proposed by each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
The grasp and record of the invention of scientific term and those skilled in the art to the prior art, can also use and this hair
Any method, equipment and the material of the similar or equivalent prior art of bright method as described in the examples, equipment, material is realized
The present invention.
Embodiment 1
In the present embodiment, product obtained is FeO (OH)/carbon nanotube magnetoelectric composites.
FeO (OH)/carbon nano tube compound material the preparation method is as follows:
(1) carbon nanotube and 56ml ethyl alcohol of the Fe(NO3)39H2O of 8.00g and 0.32g are successively added to going for 250ml
Stirring 60min in ionized water, at 25 DEG C makes it sufficiently dissolve and be uniformly mixed；
(2) step (1) acquired solution is transferred in water-bath and is cooled to room temperature after 50 DEG C of heat preservation 180min, later by liquid
Body be centrifuged after precipitating.
(3) step (2) resulting product is first cleaned 3 times with deionized water, then is cleaned 3 times with alcohol liquid.
(4) step (3) products therefrom is dried under vacuum.
The x-ray diffraction pattern of products obtained therefrom (uses irradiation source for Cu-K α in the present embodimentX-ray
Diffraction) as shown in Figure 1, it can be seen from the figure that its XRD spectrum is the characteristic spectrum of CNT.Due to CNT surface In-situ reaction
Content of material containing Fe is less, therefore cannot be tested and be characterized by XRD.
The transmission electron microscope of products obtained therefrom is as shown in Fig. 2, it can be seen from the figure that resulting materials are in carbon nanometer in the present embodiment
Pipe surface is coated with floccule, which is FeO (OH).
The XPS of products obtained therefrom schemes as shown in figure 5, can be analyzed by figure in the present embodiment, and resulting materials are FeO (OH) objects
Matter, it is consistent with TEM result.
Embodiment 2
In the present embodiment, product obtained is Fe3O4@Fe core-shell nanospheres/carbon nano tube compound material.
Fe3O4@Fe core-shell nanospheres/carbon nano tube compound material the preparation method is as follows:
(1) carbon nanotube and 60ml ethyl alcohol of the Fe(NO3)39H2O of 10.00g and 0.30g are successively added to going for 320ml
Stirring 60min in ionized water, at 25 DEG C makes it sufficiently dissolve and be uniformly mixed；
(2) step (1) acquired solution is transferred in water-bath and is cooled to room temperature after 50 DEG C of heat preservation 120min, later by liquid
Body be centrifuged after precipitating；
(3) step (2) resulting product is first cleaned 3 times with deionized water, then is cleaned 3 times with alcohol liquid；
(4) step (3) products therefrom is dried under vacuum；
(5) powder is made in hydrogen and argon gas gaseous mixture environment in step (4), is heated up with the heating rate of 5 DEG C/min
To 420 DEG C, 120min is kept the temperature, cools to room temperature with the furnace then to get product.
The x-ray diffraction pattern of products obtained therefrom (uses irradiation source for Cu-K α in the present embodimentX-ray
Diffraction) as shown in Figure 1, it can be seen from the figure that its XRD spectrum is the characteristic spectrum of CNT.Due to CNT surface In-situ reaction
Content of material containing Fe is less, therefore cannot be tested and be characterized by XRD.
The transmission electron microscope of products obtained therefrom is as shown in figure 3, it can be seen from the figure that carbon nano tube surface exists in the present embodiment
The nano particle of core-shell structure, core-shell structure centronucleus known to after analysis tem observation gained image diffraction spot is Fe simple substance
And outer layer is Fe3O4, Fe3O4@Fe nano particle is within the scope of 10-30nm.
The XPS of products obtained therefrom schemes as shown in fig. 6, can be analyzed by figure, resulting materials contain Fe in the present embodiment3O4Object phase
Ingredient, it is consistent with TEM result.
Embodiment 3
In the present embodiment, product obtained is Fe2O3Hollow nano-sphere/carbon nano tube compound material.
Fe2O3Hollow nano-sphere/carbon nano tube compound material the preparation method is as follows:
(1) carbon nanotube and 32ml ethyl alcohol of the Fe(NO3)39H2O of 6.00g and 0.20g are successively added to going for 180ml
Stirring 60min in ionized water, at 25 DEG C makes it sufficiently dissolve and be uniformly mixed；
(2) step (1) acquired solution is transferred in water-bath and is cooled to room temperature after 60 DEG C of heat preservation 90min, later by liquid
Body be centrifuged after precipitating；
(3) step (2) resulting product is first cleaned 3 times with deionized water, then is cleaned 3 times with alcohol liquid.
(4) step (3) products therefrom is dried under vacuum；
(5) powder is made in hydrogen and argon gas gaseous mixture environment in step (4), is heated up with the heating rate of 10 DEG C/min
To 400 DEG C, 120min is kept the temperature, then cools to room temperature with the furnace；
(6) powder is made in air environment in step (5), is warming up to 200 DEG C with the heating rate of 10 DEG C/min and protects
Room temperature is cooled to the furnace after warm 180min；
(7) powder is made in air environment in step (6), is warming up to 270 DEG C with the heating rate of 5 DEG C/min and keeps the temperature
90min then cools to room temperature with the furnace；
The x-ray diffraction pattern of products obtained therefrom (uses irradiation source for Cu-K α in the present embodimentX-ray
Diffraction) as shown in Figure 1, it can be seen from the figure that its XRD spectrum is the characteristic spectrum of CNT.Due to CNT surface In-situ reaction
Content of material containing Fe is less, therefore cannot be tested and be characterized by XRD.
The transmission electron microscope of products obtained therefrom is as shown in figure 4, it can be seen from the figure that carbon nano tube surface exists in the present embodiment
The nano particle of hollow structure, the hollow Nano particle known to after analysis tem observation gained image diffraction spot is Fe2O3；
Fe2O3Nano particle is within the scope of 10-30nm.
The XPS of products obtained therefrom schemes as shown in fig. 7, can be analyzed by figure, resulting materials contain Fe in the present embodiment2O3Object phase
Ingredient, it is consistent with TEM result.
Embodiment 4
The present embodiment preparation method is with embodiment 2, with embodiment 2 the difference is that in hydrogen and argon gas in the present embodiment
In gaseous mixture environment, 400 DEG C are warming up to the heating rate of 8 DEG C/min, keeps the temperature 150min.
Embodiment 5
The present embodiment preparation method is with embodiment 2, with embodiment 2 the difference is that in hydrogen and argon gas in the present embodiment
In gaseous mixture environment, 500 DEG C are warming up to the heating rate of 10 DEG C/min, keeps the temperature 60min.
Embodiment 6
The present embodiment preparation method is with embodiment 3, with embodiment 3 the difference is that in hydrogen and argon gas in the present embodiment
In gaseous mixture environment, 400 DEG C are warming up to the heating rate of 8 DEG C/min, keeps the temperature 150min.First time heat in air environment
In processing, 150 DEG C are warming up to the heating rate of 5 DEG C/min and cools to room temperature with the furnace after keeping the temperature 150min；At second of heat
In reason, 200 DEG C are warming up to the heating rate of 5 DEG C/min and cools to room temperature with the furnace after keeping the temperature 120min.
Embodiment 7
The present embodiment preparation method is with embodiment 3, with embodiment 3 the difference is that in hydrogen and argon gas in the present embodiment
In gaseous mixture environment, 500 DEG C are warming up to the heating rate of 10 DEG C/min, keeps the temperature 60min.First time heat in air environment
In processing, 170 DEG C are warming up to the heating rate of 1 DEG C/min and cools to room temperature with the furnace after keeping the temperature 90min, be heat-treated for second
In, 300 DEG C are warming up to the heating rate of 1 DEG C/min and cool to room temperature with the furnace after keeping the temperature 60min.
Performance test
1, specific surface area
In N2Under atmosphere is enclosed, material made from Quad-rasorb-SI instrument record embodiment 1 to embodiment 3 is respectively adopted
Nitrogen adsorption-release profiles, and with Brunauer-Emmett-Teller (BET) method measurement sample specific surface area.As a result such as
Shown in Fig. 8, it can be seen from the figure that nano electromagnetic composite wave-suction material obtained by embodiment 1 to embodiment 3 all have it is higher
Specific surface area, be conducive to improve composite material microwave absorbing property.The wherein obtained Fe of embodiment 23O4@Fe nucleocapsid is received
Rice ball/carbon nano tube compound material has maximum specific surface area 116m2/ g, this is beneficial to the impedance of optimization composite material
Match, to improve the absorbing property of composite material.
2, nano electromagnetic composite wave-suction material of the difference Example 1 into embodiment 3, is respectively distributed in paraffin, makes
The gross mass percentage that composite wave-suction material accounts for composite wave-suction material and paraffin is 25%, is pressed into that outer diameter is 7.0mm, internal diameter is
The annular element of 3.04mm, different-thickness (0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm., 4.5mm, 5mm),
Using Agilent N5224A vector network analyzer, the complex dielectric permittivity and complex permeability of coaxial axis method measurement electromagnetic parameter are used
Electromagnetic parameter, test frequency range be 2-18GHz, obtained reflection loss with frequency change curve such as Fig. 9 to Figure 11
Shown, the results are shown in Table 1.
Table 1
Symbol meaning is as follows: RLminMinimal reflection loss.
From Fig. 9 to Figure 11 and table 1 can be seen that 1 products therefrom FeO (OH) of embodiment/carbon nano tube compound material in institute
Frequency-division section RL value is less than -10dB inside measured frequency range but its RL value is higher, although having its property of certain absorbing property
It can be to be improved.2 products therefrom Fe of embodiment3O4@Fe core-shell nanospheres/carbon nanotube sample thickness range is 0.5~5mm,
Inhaling wavestrip wide (RL < -10dB) is 4.0~10.8GHz and 11.2~18.0GHz, is 13.1GHz in frequency, sample thickness is
When 2.0mm, RLminFor -42.9dB；3 products therefrom Fe of embodiment2O3Hollow nano-sphere/carbon nano tube compound material sample thickness
Range is 0.5~5mm, and inhaling wavestrip wide (RL < -10dB) is 2.1~3.9GHz and 4.8~18GHz, is 5.5GHz in frequency,
When sample thickness is 4.5mm, RLminFor -24.7dB.It can be seen that 2 products therefrom of embodiment at C-Ku frequency band (4-18GHz)
More excellent absorbing property is shown in range, and there is very big application potential.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of preparation method of carbon nanotube base Electromagnetic heating absorbing material, which is characterized in that it is at least included the following steps:
1) FeO (OH)/carbon nano tube compound material preparation:
A., ferric nitrate, carbon nanotube are added to the in the mixed solvent of ethyl alcohol and water, stirred；
B. acquired solution in the step a is heated, carries out processing after reaction and obtains FeO (the OH)/carbon nanometer
Pipe composite material；
2)Fe3O4@Fe core-shell nanospheres/carbon nano tube compound material preparation: by FeO (OH)/carbon obtained in the step 1)
Nanometer tube composite materials are heat-treated, are cooled to room temperature under hydrogen or hydrogen and argon gas mixed-gas environment, are obtained
Fe3O4@Fe core-shell nanospheres/carbon nano tube compound material.
2. a kind of preparation method of carbon nanotube base Electromagnetic heating absorbing material, which is characterized in that it is at least included the following steps:
1) FeO (OH)/carbon nano tube compound material preparation:
A., ferric nitrate, carbon nanotube are added to the in the mixed solvent of ethyl alcohol and water, stirred；
B. acquired solution in the step a is heated, carries out processing after reaction and obtains FeO (the OH)/carbon nanometer
Pipe composite material；
2)Fe2O3The preparation of hollow nano-sphere/carbon nano tube compound material: FeO (OH)/carbon obtained in the step 1) is received
Mitron composite material is heat-treated in hydrogen and argon gas gaseous mixture, is carried out respectively in air or oxygen after heat treatment
Heat treatment for the first time and second of heat treatment, are cooled to room temperature, obtain Fe2O3Hollow nano-sphere/carbon nano tube compound material.
3. a kind of preparation method of carbon nanotube base Electromagnetic heating absorbing material according to claim 1, which is characterized in that its
Any one or multinomial including following technical characteristic:
Ferric nitrate in the step 1), carbon nanotube, water, ethyl alcohol mass ratio be 1:(0.01~0.04): (30~35): (8~
10)；
Heating reaction temperature is 40~80 DEG C in the step 1), and the reaction time is 30~240min.
4. a kind of preparation method of carbon nanotube base Electromagnetic heating absorbing material according to claim 1, which is characterized in that institute
Stating the temperature being heat-treated in step 2) is 400~500 DEG C, and soaking time is 60~150min, heating rate is 5~10 DEG C/
min。
5. a kind of preparation method of carbon nanotube base Electromagnetic heating absorbing material according to claim 2, which is characterized in that its
Any one or multinomial including following technical characteristic:
Ferric nitrate in the step 1), carbon nanotube, water, ethyl alcohol mass ratio be 1:(0.01~0.04): (30~35): (8~
10)；
Heating reaction temperature is 40~80 DEG C in the step 1), and the reaction time is 30~240min.
6. a kind of preparation method of carbon nanotube base Electromagnetic heating absorbing material according to claim 2, which is characterized in that its
Any one or multinomial including following technical characteristic:
Heat treatment temperature in the step 2) in hydrogen and argon gas gaseous mixture is 400~450 DEG C, soaking time is 90~
150min, heating rate are 1~10 DEG C/min；
The heat treatment temperature of the first time heat treatment carried out in air or oxygen in the step 2) is 150~200 DEG C, heat preservation
Time is 90~180min, and heating rate is 1~10 DEG C/min；
The heat treatment temperature of second of the heat treatment carried out in air or oxygen in the step 2) is 200~300 DEG C, heat preservation
Time is 60~120min, and heating rate is 1~10 DEG C/min.
7. Fe prepared by claim 1 or 3 or 4 preparation methods3O4@Fe core-shell nanospheres/carbon nano tube compound material.
8. Fe prepared by claim 2 or 5 or 6 preparation methods2O3Hollow nano-sphere/carbon nano tube compound material.
9. purposes of the carbon nanotube base Electromagnetic heating absorbing material in electromagnetic wave absorbent material field described in claim 7.
10. purposes of the carbon nanotube base Electromagnetic heating absorbing material in electromagnetic wave absorbent material field described in claim 8.
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