CN113249090A - Composite material and preparation method and application thereof - Google Patents
Composite material and preparation method and application thereof Download PDFInfo
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- CN113249090A CN113249090A CN202110530175.3A CN202110530175A CN113249090A CN 113249090 A CN113249090 A CN 113249090A CN 202110530175 A CN202110530175 A CN 202110530175A CN 113249090 A CN113249090 A CN 113249090A
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002063 nanoring Substances 0.000 claims abstract description 38
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000011358 absorbing material Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000012692 Fe precursor Substances 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 235000010339 sodium tetraborate Nutrition 0.000 claims 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical group [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GOCYOWTYSKXMTR-UHFFFAOYSA-N trisodium borate dihydrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]B([O-])[O-] GOCYOWTYSKXMTR-UHFFFAOYSA-N 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- FVJFRFUSHCIRKP-UHFFFAOYSA-N disodium;hydrogen borate Chemical group [Na+].[Na+].OB([O-])[O-] FVJFRFUSHCIRKP-UHFFFAOYSA-N 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001093 holography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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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
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Hard Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the field of functional materials, and particularly relates to a composite material and a preparation method and application thereof. A composite material is prepared from carbon source and Fe3O4And mixing the nanorings, and calcining to carbonize to obtain the composite material. The preparation method of the composite material has the characteristics of stability, high repeatability, simplicity and easiness in operation, and experiments prove that the composite material has the characteristics of low cost, wide sources, thin thickness, wide absorption frequency band, light load and strong absorption capacity.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a composite material and a preparation method and application thereof.
Background
In modern society, with continuous development and innovation of science and technology, various electronic devices, such as mobile phones, intelligent robots and 5G base stations, continuously appear. These electronic devices offer convenience to the human society, however, they also cause a great deal of electromagnetic pollution, negatively affecting the environment and the normal operation of the electronic devices, and further, they are constantly threatening the health of people. Therefore, in order to solve the problem, it is very important to research and prepare a wave-absorbing material with a large wave-absorbing bandwidth, a strong reflection loss, a low matching thickness and a low filling ratio. Electromagnetic absorbing materials can be classified into three major categories, namely, conductive materials, dielectric materials and magnetic materials, according to the loss characteristics of electromagnetic waves. Hitherto, carbon materials and magnetic metal materials have been widely used for the preparation of electromagnetic absorption materials, and great research results have been obtained.
In the magnetic material, ferrite is a more widely researched and developed one, has a dielectric loss and magnetic loss double loss mechanism, has resistivity far larger than that of metal and alloy thereof, and can avoid the skin effect of a metal conductor due to larger conductivity, so that higher magnetic conductivity can be kept under high frequency. Fe3O4The ferrite is the most typical ferrite, has the advantages of abundant natural resources, no pollution to the environment, simple preparation process, strong wave-absorbing strength and the like, and is widely concerned by people all the time. However, the wave-absorbing material has the defects of large density, narrow absorption frequency band and the like, so that the application of the wave-absorbing material is limited to a certain extent, and therefore, two solutions are provided for ensuring that the wave-absorbing material can meet the comprehensive performance requirements of thinness, lightness, width and strength. Firstly, the prepared nano materials with different morphologies have large specific surface area of nano particles with special morphology, can cause multiple scattering, have more surface dangling bonds, and a large number of dangling bonds can cause the enhancement of interface polarization, so that the scattering and polarization can effectively increase the absorption attenuation of the material to electromagnetic waves and improve the wave absorbing performance of the material; another method is to reduce Fe3O4When the size of the particles reaches the nanometer level, the particles have special properties different from the conventional bulk materials due to the influences of the surface effect, small-size effect, quantum effect, macroscopic quantum tunneling effect and the like of the nanoparticles. Similarly, when the size reaches the nanometer level, the surface area is large, the interface polarization is enhanced, and the wave absorbing performance is good. However, how to prepare Fe with special morphology by a simple and convenient method3O4The electromagnetic absorbing material of (2) still presents certain difficulties.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a composite material, a method for its preparation and use, which solve the problems of the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
One of the purposes of the invention is to provide a preparation method of a composite material, which comprises the following steps: mixing a carbon source with Fe3O4And mixing the nanorings, and calcining to carbonize to obtain the composite material.
Preferably, the carbon source is a polyvinylpyrrolidone aqueous solution, and the concentration of the polyvinylpyrrolidone aqueous solution is 1-50 mg/ml.
More preferably, the molecular weight of the polyvinylpyrrolidone is 30000-100000.
Preferably, the calcining temperature is 200-800 ℃.
More preferably, the temperature of the calcination is 400-600 ℃.
In the application, the calcining temperature cannot be too high or too low, and if the calcining temperature is too high, the dielectric constant is improved, the impedance is mismatched, and the wave-absorbing performance is reduced; if the calcination temperature is too low, insufficient carbonization may result, resulting in a decrease in the wave-absorbing properties. Therefore, the calcination temperature is preferably 400 to 600 ℃ in the present application.
Preferably, the temperature rise rate of the calcination is 1-10 ℃/min.
More preferably, the temperature rise rate of the calcination is 3-7 ℃/min.
Preferably, the calcining time is 30-120 min.
More preferably, the calcining time is 40-80 min.
Preferably, the calcination is carried out in a protective atmosphere.
More preferably, the protective atmosphere is one or both of hydrogen and nitrogen.
Preferably, the carbon source is in combination with Fe3O4The mass ratio of the nanorings is (2-8): 1.
more preferably, the carbon source is in combination with Fe3O4The mass ratio of the nanorings is (2-6): 1.
preferably, the carbon source, Fe3O4Mixing the nano-ring and water, centrifuging, washing, drying and calcining.
More preferably, the Fe3O4The mass ratio of the nano-ring to the water is 1: (150-250).
More preferably, the washing is performed by washing with water for 1-10 times.
More preferably, the drying temperature is 40-100 ℃.
Preferably, the Fe3O4The nanoring is hollow cylinder, the inner diameter of the cylinder is 100-200 nm, the outer diameter of the cylinder is 200-300nm, and the height of the cylinder is 50-150 nm.
Preferably, the Fe3O4The preparation method of the nano ring comprises the following steps: mixing an iron precursor, water, a surfactant and a cosolvent, carrying out hydrothermal reaction, and sintering to obtain the Fe3O4And (4) a nano ring.
More preferably, the iron precursor is ferric chloride.
More preferably, the co-solvent is sodium sulfate.
More preferably, the surfactant is sodium hydrogen borate.
Further preferably, the surfactant is sodium borate dihydrate.
More preferably, the mass ratio of the iron precursor, the water, the surfactant and the cosolvent is (0.8-1.2): (180-220): (0.003-0.007): (0.01-0.02).
Further preferably, the mass ratio of the iron precursor, the water, the surfactant and the cosolvent is (1.0-1.2): (190-210): (0.004-0.006): (0.01-0.02).
More preferably, the temperature of the hydrothermal reaction is 180-220 ℃.
Further preferably, the temperature of the hydrothermal reaction is 200 to 220 ℃.
More preferably, the hydrothermal reaction time is 24-48 h.
Further preferably, the hydrothermal reaction time is 40-48 h.
More preferably, the sintering temperature is 200-800 ℃.
Further preferably, the sintering temperature is 400-600 ℃.
More preferably, the sintering time is 60-150 min.
Further preferably, the sintering time is 80-120 min.
More preferably, the sintering is performed in a protective atmosphere.
Further preferably, the protective atmosphere is one or both of hydrogen and nitrogen.
More preferably, the iron precursor, the water, the surfactant and the cosolvent are mixed at 10-40 ℃ for 20 min-150 mim, and then hydrothermal reaction is carried out.
More preferably, the hydrothermal reaction further comprises centrifugation, washing and drying.
Further preferably, the washing is 1 to 10 times with water.
Further preferably, the drying temperature is 40-100 ℃.
The second purpose of the invention is to provide the composite material prepared by the preparation method.
Preferably, the composite material is made of Fe3O4The nano ring is wrapped with a carbon layer; the carbon layer has a thickness of 4-5 nm.
The invention also aims to provide the application of the composite material as a wave-absorbing material in the field of electromagnetic waves.
The method takes ferric chloride as a precursor to prepare Fe3O4Nanorings, coating Fe with PVP3O4Nano-ring, then calcining and carbonizing to obtain carbon-coated Fe3O4The composite material of the nano-ring improves the wave absorbing performance of the composite material. Experiments prove that the preparation method has the characteristics of stability, controllability, simplicity and easiness in operation, the obtained composite material has the electromagnetic wave absorption characteristics of thin thickness, wide absorption frequency band, light load and strong absorption capacity, and the magnetic vortex phenomenon is observed through the electronic holography.
Compared with the prior art, the invention has the following beneficial effects:
1) the preparation method of the composite material has the characteristics of stability, high repeatability, simplicity and easiness in operation.
2) The composite material prepared by the method has the characteristics of thin thickness, wide absorption frequency band, light load and strong absorption capacity.
Drawings
Figure 1 shows XRD patterns of example 1, example 2 and example 3.
Fig. 2 shows TEM images of example 3 and example 1.
Wherein the reference numerals in fig. 2 are as follows: a-1 is a TEM image of example 1, a-2 is an HRTEM image of example 1, b-1 is a TEM image of example 3, and b-2 is an HRTEM image of example 3.
Fig. 3 is a wave-absorbing performance diagram of example 1, example 2 and example 3.
FIG. 4 shows a microscopic magnetic structure of example 3.
Fig. 5 shows hysteresis curves of example 3 and example 1.
Wherein the reference numerals in fig. 5 are as follows: FNR corresponds to example 1, and FNR-C corresponds to example 3.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
In the examples of the present application, the products obtained by the preparation of each example and comparative example were irradiated with an irradiation source of Cu-Ka (K) ((K))
) To determine the crystal structure.
In the examples of the present application, the morphology of the product obtained by each example and comparative example was observed by a projection electron microscope (TEM) and a high-resolution transmission electron microscope (HRTEM).
In the examples of the present application, the products obtained for each of the examples and comparative examples were uniformly dispersed in paraffin wax, which was 25% by weight based on the total weight, and then pressed by a die into coaxial sample rings having an outer diameter of 7.0mm and an inner diameter of 3.04 mm. The electrical complex permittivity and complex permeability of the material are measured by adopting a Ceyear 3672B-S vector network analyzer according to the technical requirements of coaxial line transmission/reflection measurement in American society for testing and materials standard ASTM D7449/D7449M-08, and the RL value of the material is calculated according to the transmission line theory.
In the embodiment of the application, the microscopic magnetic structure of the material is observed by adopting the electronic holographic technology.
In the embodiment of the application, a magnetic hysteresis chart is obtained by analyzing the magnetic property of a material through a JDAW-2000CAD type vibration sample magnetometer.
In the embodiment of the application, polyvinylpyrrolidone is used as a carbon source, and the molecular weight of polyvinylpyrrolidone is 60000.
Example 1
In example 1, Fe was prepared3O4The nanoring comprises the following steps:
1.08g of ferric chloride hexahydrate, 5.6mg of sodium borate dihydrate and 15.6mg of sodium sulfate were added to 200ml of deionized water in sequence, and stirred at 25 ℃ for 40 minutes to be sufficiently dissolved and uniformly mixed, thereby obtaining a mixed solution.
Transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 48 hours at 220 ℃. Centrifuging the prepared sample, washing the sample with deionized water for three times, placing the sample in a 60 ℃ oven, and drying the sample for 24 hours; then roasting at 500 ℃ for 120min in hydrogen/nitrogen atmosphere, wherein the heating rate of the roasting is 5 ℃/min, and cooling to room temperature along with the furnace to obtain Fe3O4And (4) a nano ring.
Example 2
In this example 2, the Fe prepared in example 1 was encapsulated with PVP3O4The nanoring comprises the following steps:
0.1g of Fe from example 1 was weighed3O4Adding nanoring and 0.5g PVP into 20ml deionized water, stirring for 12h, centrifuging, washing with deionized water for three times, placing in a 60 ℃ oven, drying for 24h to obtain PVP coated Fe3O4The material of the nanoring.
Example 3
In example 3, the Fe prepared in example 1 was coated with carbon3O4Nanorings to prepare a composite material comprising the steps of:
0.1g of Fe of example 13O4Adding nanorings and 0.5g of PVP into 20ml of water, stirring for 12h, centrifuging, washing for 3 times by using deionized water, and drying for 24h at 60 ℃; then placing the composite material in an argon atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, preserving the heat for 60min, and cooling to room temperature along with the furnace to obtain the composite material.
The composite material obtained in this example was made of Fe3O4The nano ring is wrapped by a carbon layer, and the thickness of the carbon layer is 4 nm.
FIG. 1 is an XRD pattern for example 1, example 2 and example 3; FIG. 2 is TEM images of example 1, example 2 and example 3; FIG. 3 is a wave-absorbing property diagram of examples 1, 2 and 3; table 1 shows the wave-absorbing performance data of example 1, example 2 and example 3; FIG. 4 is a view showing a microscopic magnetic structure of example 3; fig. 5 is hysteresis charts of examples 1 and 3.
TABLE 1
From the XRD pattern of FIG. 1, Fe was observed in all of examples 1, 2 and 33O4Is Fe at values of 18.3 °, 30.1 °, 35.5 °, 37.1 °, 43.1 °, 53.5 °, 57.0 °, 62.6 ° and 74.1 °, respectively3O4The (111), (220), (311), (222), (400), (422), (511), (440), and (533) crystal planes of (A).
As can be seen from the TEM image of FIG. 2, a-1 and a-2 are Fe, respectively3O4TEM and HRTEM images of nanorings, Fe3O4The nanoring is hollow cylinder, the inner diameter of the cylinder is 150nm, the outer diameter of the cylinder is 200nm, and the height of the cylinder is 100 nm. In the figure, b-1 and b-2 are respectively Fe3O4TEM and HRTEM images of composite material with carbon layer wrapped outside nano ring, the composite material is in core-shell structure and Fe is wrapped by carbon3O4And (4) a nano ring.
As can be seen from table 1 and fig. 3: the RLmin values of the embodiments 1, 2 and 3 in the tested frequency range are all less than-10 dB, namely the RLmin values have good wave absorbing performance. Fe of example 13O4When the thickness of the nano ring is 1.5mm, the wave-absorbing bandwidth (RL) of the nano ring is<-10dB) of 12.8-17.8GHz, RLmin of-27.7 dB; the material of example 2 has a wave absorbing bandwidth (RL) at a test thickness of 4.0mm<-10dB) is 4.8-7.9GHz, RLmin is-48.3 dB; the composite material obtained in example 3 has a wave-absorbing bandwidth (RL) of 1.5mm<-10dB) is 14.9-18.0GHz and RLmin is-61.5 dB. Therefore, the composite material obtained in the example 3 shows excellent wave-absorbing performance in a test range and has great application potential, probably because the interface polarization is improved by the coating of carbon, and simultaneouslyThe impedance matching of the material is also adjusted, thereby improving the electromagnetic wave absorption performance of the composite material.
From the microscopic magnetic structure diagram of fig. 4, it can be seen that the composite material prepared by the present application has a distinct magnetic vortex structure.
As is clear from the hysteresis loop chart of FIG. 5, the saturation magnetization and the coercive force values of examples 1 and 3 were 70.61emu g, respectively-1And 67.35emu g-1Coercive values of 230Oe and 190Oe, respectively, indicating Fe3O4The nano ring is wrapped by a carbon layer and then is Fe3O4The magnetic properties of the nanorings are slightly degraded.
In conclusion, Fe with excellent wave-absorbing performance can be prepared through simple chemical reaction and heat treatment3O4A nanoring composite. Especially, the process parameters can effectively adjust Fe3O4The particle phase composition and microstructure of the nano-ring composite material finally regulate and control the performance of the nano-ring composite material, thereby greatly promoting the industrial production and having important significance for the wide application and development of the wave-absorbing material.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the composite material is characterized by comprising the following steps:
mixing a carbon source with Fe3O4And mixing the nanorings, and calcining to carbonize to obtain the composite material.
2. The method according to claim 1, wherein the carbon source is an aqueous solution of polyvinylpyrrolidone, and the concentration of the aqueous solution of polyvinylpyrrolidone is 1 to 50 mg/ml.
3. The preparation method according to claim 1, wherein the temperature of the calcination is 200 to 800 ℃;
and/or the temperature rise rate of the calcination is 1-10 ℃/min;
and/or the calcining time is 30-120 min;
and/or the carbon source is reacted with Fe3O4The mass ratio of the nano-ring is (2-8): 1.
4. the method of claim 1, wherein the Fe is3O4The nanoring is hollow cylinder, the inner diameter of the cylinder is 100-200 nm, the outer diameter of the cylinder is 200-300nm, and the height of the cylinder is 50-150 nm.
5. The method according to claim 4, wherein the Fe3O4The preparation method of the nano ring comprises the following steps: mixing an iron precursor, water, a surfactant and a cosolvent, carrying out hydrothermal reaction, and sintering to obtain the Fe3O4And (4) a nano ring.
6. The method according to claim 5, wherein the iron precursor is ferric chloride;
and/or, the cosolvent is sodium sulfate;
and/or the surfactant is sodium borate;
and/or the mass ratio of the iron precursor, the water, the surfactant and the cosolvent is (0.8-1.2): (180-220): (0.003-0.007): (0.01-0.02).
7. The preparation method according to claim 5, wherein the temperature of the hydrothermal reaction is 180-220 ℃;
and/or the time of the hydrothermal reaction is 24-48 h.
And/or the sintering temperature is 200-800 ℃;
and/or the sintering time is 60-150 min.
8. A composite material produced by the production method according to any one of claims 1 to 7.
9. The composite material of claim 8, wherein the composite material is made of Fe3O4The nano ring is wrapped with a carbon layer; the carbon layer has a thickness of 4-5 nm.
10. Use of the composite material according to claim 8 as a wave-absorbing material in the field of electromagnetic waves.
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| CN105152226A (en) * | 2015-08-21 | 2015-12-16 | 浙江师范大学 | Preparation and application of magnetic nanoring microwave absorbing agent |
| CN106241886A (en) * | 2016-07-22 | 2016-12-21 | 浙江师范大学 | A kind of Electromagnetic enhancement carbon magnetic composite and preparation method and application |
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| CN105152226A (en) * | 2015-08-21 | 2015-12-16 | 浙江师范大学 | Preparation and application of magnetic nanoring microwave absorbing agent |
| CN106241886A (en) * | 2016-07-22 | 2016-12-21 | 浙江师范大学 | A kind of Electromagnetic enhancement carbon magnetic composite and preparation method and application |
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