CN114433860B - Micron-scale fleshy porous iron-cobalt alloy and preparation and application thereof - Google Patents
Micron-scale fleshy porous iron-cobalt alloy and preparation and application thereof Download PDFInfo
- Publication number
- CN114433860B CN114433860B CN202111576060.4A CN202111576060A CN114433860B CN 114433860 B CN114433860 B CN 114433860B CN 202111576060 A CN202111576060 A CN 202111576060A CN 114433860 B CN114433860 B CN 114433860B
- Authority
- CN
- China
- Prior art keywords
- fleshy
- cobalt alloy
- iron
- scale
- micron
- 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.)
- Active
Links
- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 48
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011358 absorbing material Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 8
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 abstract description 24
- 239000000956 alloy Substances 0.000 abstract description 18
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 230000035699 permeability Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 10
- 229910017061 Fe Co Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000005381 magnetic domain Effects 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 235000013372 meat Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 229910002546 FeCo Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 1
- -1 cobalt iron oxyhydroxide Chemical compound 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
- H01Q17/008—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems with a particular shape
-
- 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
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention relates to a micron-scale fleshy porous iron-cobalt alloy and preparation and application thereof, and the micron-scale fleshy porous iron-cobalt alloy is successfully constructed through a convenient hydrothermal reaction-hydrogen-argon reduction synthesis strategy. The stable vortex domain structure can improve the magnetic storage capacity, and the intense movement of magnetic moment is helpful to improve the magnetic loss capacity, so that the material has higher complex permeability. The porous structure increases multiple scattering and optimizes impedance matching. Therefore, compared with the prior art, the effective absorption bandwidth of the fleshy iron-cobalt alloy material reaches 5.7GHz, the maximum reflection loss is 53.8dB, and the fleshy iron-cobalt alloy material shows excellent electromagnetic wave loss capacity in the frequency range of 2.0-18.0 GHz.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and relates to a micrometer-scale fleshy porous iron-cobalt alloy, and preparation and application thereof.
Background
With the rapid development of science and technology and the advent of the information age, various electronic devices and electronic appliances have been closely related to our lives. While enjoying the convenience brought by people, the problems of increasingly serious electromagnetic interference, electromagnetic pollution and the like cannot be ignored. The electronic equipment in industrial and household environments is added with a plurality of electromagnetic wave emission sources and receivers, which causes electromagnetic interference and electromagnetic pollution, thus not only affecting the normal use of the electronic equipment, but also possibly endangering the health of human beings and other organisms. Microwave absorbing materials have been developed to reduce electromagnetic interference and electromagnetic pollution. The loss mechanism of the wave absorbing material to the electromagnetic wave is mainly divided into magnetic loss mainly based on magnetic medium and dielectric loss contributed by dielectric medium and electric conductor. The magnetic material has the characteristics of double loss mechanism and the like, and is widely applied in the field of electromagnetic wave absorption. The magnetic transition metal and alloy materials, such as iron, cobalt, nickel, iron-cobalt alloy, etc., have intrinsic ferromagnetic characteristics, such as strong saturation magnetization, high Curie temperature, spontaneous magnetization, magnetocrystalline anisotropy, etc., which are favorable for the dissipation of electromagnetic waves and the improvement of microwave absorption performance.
FeCo alloys are important metallic soft magnetic materials that are of interest due to their unique properties of high saturation induction, low coercivity, high permeability, and low magnetic anisotropy constants. The excellent properties lead the iron-cobalt alloy to be widely applied in the fields of magnetic recording materials, wave absorbing materials, biotechnology, catalytic materials, hard alloy materials and the like. However, the existing iron-cobalt alloy wave absorbing material is generally of a non-porous structure, and the performance of the existing iron-cobalt alloy wave absorbing material in the aspects of electromagnetic wave absorption and the like still has a large room for improvement.
Disclosure of Invention
The invention aims to provide a micron-scale fleshy porous iron-cobalt alloy, and preparation and application thereof.
It has been found through research that single-component magnetic metal or alloy materials as microwave absorbers still face some obstacles. For example, the disadvantages of narrow absorption bandwidth, reduced reflection attenuation, thick coating, etc., have prevented their practical use. In addition, the magnetic nanoparticles currently under investigation have size limitations and a single magnetic domain structure, often exhibiting relatively weak magnetic losses. In contrast, the assembly of the magnetic transition metal alloy material can realize controllable anisotropy, change the magnetic domain topological structure and is beneficial to improving the complex permeability. Based on the method, the micron-scale fleshy porous iron-cobalt alloy material is prepared. By adjusting the hydrothermal reaction time during the preparation of the precursor, the microstructure of the iron-cobalt alloy can be greatly changed, and the structure can influence the electromagnetic parameters and impedance matching characteristics of substances, so that the aim of accurately regulating the wave absorbing performance of the magnetic material is finally achieved. Wherein, the stable combination of a plurality of vortex domains is favorable for improving the magnetic storage capacity and the magnetic loss capacity and enhancing the attenuation capacity of the iron-cobalt alloy to electromagnetic waves.
The invention synthesizes the precursor cobalt iron oxyhydroxide by adopting a high-efficiency and simple hydrothermal reaction method. After high-temperature reduction in hydrogen argon atmosphere, the product particles have better dispersibility and no obvious agglomeration phenomenon. Meanwhile, the porous iron-cobalt alloy with the meat shape has excellent comprehensive performance in the field of microwave absorption.
The aim of the invention can be achieved by the following technical scheme:
One of the technical schemes of the invention provides a preparation method of a micron-scale fleshy porous iron-cobalt alloy, which comprises the following steps:
(1) Adding ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ammonium fluoride and urea into deionized water, stirring and dissolving to obtain a transparent light pink mixed solution;
(2) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction, washing and drying the obtained reaction product to obtain orange precursor powder;
(3) And (3) placing the precursor powder in an argon hydrogen atmosphere for high-temperature reduction, and then cooling to room temperature to obtain a target product.
Further, in the step (1), the molar ratio of ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ammonium fluoride and urea is (1-3): (1-4): (4-10): (12-18).
Further, in the step (1), the addition amount of deionized water satisfies the following conditions: the concentration of Fe 3+ in the mixed solution is 0.01-0.03 mol/L.
Further, in the step (2), the temperature of the hydrothermal reaction is 80-140 ℃ and the time is 40-80 min.
Further, in the step (2), the washing process is as follows: and adopting deionized water and ethanol to centrifugally wash for a plurality of times at 8000-10000 rpm.
Further, in the step (2), the drying process specifically includes: vacuum drying at 60-80 deg.c.
Further, in the step (3), the volume fraction of hydrogen in the hydrogen argon atmosphere is 4-6%.
Further, in the step (3), the high-temperature reduction process specifically includes: calcining at 550-650 deg.c for 1-3 hr.
The second technical scheme of the invention provides a micron-scale fleshy porous iron-cobalt alloy which is prepared by adopting the preparation method, wherein the porous iron-cobalt alloy is fleshy, has the size of about 2-3 mu m and has a nano-pore structure distributed on the surface.
The third technical proposal of the invention provides the application of the porous Fe-Co alloy with micron scale and fleshy, which is used as the microwave absorbing material. In particular to be used as an electromagnetic wave absorbing material. When the method is applied specifically, the steps are as follows: the prepared iron-cobalt alloy powder was uniformly mixed with the slice paraffin at a mass ratio of 1:1. The mixture was poured into an aluminum mold and pressed into a circular ring sample having an inner diameter of 3.0mm, an outer diameter of 7.0mm and a thickness of 2.0 mm. Complex relative permittivity and permeability in the range of 2.0-18.0GHz were tested using a vector network analyzer model N5230C.
Compared with the prior art, the micron-scale fleshy porous iron-cobalt alloy has the characteristics of high absorption intensity and wide response frequency band, and the domain wall is basically stable due to the fact that the center of a vortex domain slightly moves along with a magnetic field, so that the magnetic storage capacity is improved; the magnetic vector near the domain wall vibrates vigorously, has stronger natural resonance and domain wall resonance effects, and improves the magnetic loss capability. The strong magnetic coupling action between the structural units increases the complex permeability and enhances the magnetic loss. The rich pore structure increases multiple scattering and multiple reflection, further optimizing impedance matching. The porous iron-cobalt alloy with the meat shape with the micrometer scale has good electromagnetic wave absorption performance, strong magnetism and easy preparation and has good application prospect.
Drawings
FIG. 1 is a scanning electron microscope and a transmission electron microscope of examples 1 to 4: (a1) Example 1-scanning electron microscope image of a fleshy iron-cobalt alloy; (a2) Example 1-transmission electron microscopy of a fleshy iron-cobalt alloy; (b 1) scanning electron microscopy of the example 2-spherical iron-cobalt alloy; (b 2) a transmission electron micrograph of the spherical iron-cobalt alloy of example 2; (c1) Example 3-scanning electron microscopy of near fleshy iron-cobalt alloy; (c2) Example 3-transmission electron microscopy of near fleshy iron-cobalt alloy; (d1) Example 4-scanning electron microscopy of too much meat-like iron-cobalt alloy; (d2) Example 4-transmission electron microscopy of too much meat-like iron-cobalt alloy.
FIG. 2 is an X-ray diffraction pattern of the fleshy Fe-Co alloy of example 1.
Fig. 3 is a graph of the relative complex permeability, including real and imaginary parts of complex permeability, of the example 1-fleshy iron-cobalt alloy.
FIG. 4 is a graph showing the relative complex permittivity of the example 1-fleshy iron-cobalt alloy, including real and imaginary parts of the complex permittivity.
FIG. 5 shows the reflection loss values at a thickness of 2.0mm for examples 1-4.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise indicated, materials or processing techniques are all typical of those commercially available in the art.
Example 1:
Preparing the micron-scale fleshy porous iron-cobalt alloy:
Firstly, 1mmol Fe(NO3)3·9H2O,3mmol Co(NO3)2·6H2O,8mmol NH4F,15mmol CO(NH2)2, are respectively weighed and added into 50mL of deionized water, and the deionized water is completely dissolved under intense magnetic stirring, so that a uniform and transparent light pink solution is obtained.
Next, the solution was transferred to a teflon lined stainless steel hot-water reactor and heated at 120 ℃ for 1 hour. After cooling to room temperature, centrifugal washing is carried out for a plurality of times by deionized water and ethanol, vacuum drying is carried out at 60 ℃, and orange Fe xCo1-x OOH precursor is obtained after collection.
And finally, placing the precursor powder into a porcelain boat, placing the porcelain boat into a tube furnace, reducing the porcelain boat at a high temperature of 600 ℃ for 2 hours under hydrogen-argon atmosphere (the hydrogen volume fraction is 5%), and naturally cooling the porcelain boat to room temperature at a heating rate of 2 ℃/min -1 to obtain the micron-sized porous iron-cobalt alloy black powder. The appearance is similar to meat shape, the size is about 2-3 mu m, and the surface is provided with uniformly distributed nano-pore structures.
Example 2:
Compared to example 1, the vast majority are identical, except in this example: the hydrothermal reaction time was changed to 20 minutes.
Example 3:
Compared to example 1, the vast majority are identical, except in this example: the hydrothermal time was 40 minutes.
Example 4:
compared to example 1, the vast majority are identical, except in this example: the hydrothermal time was 80 minutes.
The microcosmic morphology of the morphology-controllable microscale multi-meat-like porous iron-cobalt alloy in the above examples was characterized by scanning electron microscopy (SEM, hitachi FE-SEM S-4800), and a powder sample was coated on the surface of the conductive paste for testing. The microstructure information of a series of alloy materials is characterized by a transmission electron microscope (TEM, JEOL JEM-2100F), and powder samples are subjected to ultrasonic dispersion in ethanol and then are dripped on a carbon-supported copper mesh for drying and testing. The X-ray diffraction spectrum was measured by BrukerD a 8 Advance instrument. And (3) testing complex relative magnetic permeability and complex relative dielectric constant in the range of 2.0-18.0GHz by using a vector network analyzer with the model of N5230C, and obtaining reflection loss values under different thicknesses through calculation fitting.
FIG. 1 is a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) of the multi-meat-shaped porous iron-cobalt alloy synthesized in the above examples 1-4, wherein the morphology of example 1 is similar to that of multi-meat, the size is about 2-3 μm, and the surface has a uniformly distributed nano-pore structure. The particle size distribution of the sample is uniform, and the particle dispersibility is good. Example 2 was spherical in morphology, approximately 2-3 μm in size, with a uniformly distributed nanoporous structure on the surface. Compared to example 1, example 2 did not evolve to be fleshy due to the reduced hydrothermal time, and the magnetic domain structure was relatively single. Example 3 was similar in morphology to an unformed fleshy, with dimensions of about 2-3 μm, with a uniformly distributed nanopore structure on the surface. Example 4 was similar to an overcooked fleshy shape in appearance, with dimensions of about 2-3 μm, and the pore size of the nanopores was greater than that of examples 1-3, with cracks appearing on the surface. Therefore, the hydrothermal reaction time is an important condition for morphology evolution.
FIG. 2 is an X-ray diffraction (XRD) analysis of the porous Fe-Co-based multi-meat alloy of example 1 above. In the figure, diffraction peaks at 2θ=44.75 °,65.13 °, and 82.45 ° correspond to the (110), (200), and (211) crystal planes of simple cubic FeCo (JCPDS No. 49-1567). XRD pattern analysis demonstrates the compositional information of the material and no significant impurities and miscibility are present.
Fig. 3 is a real part (μ ') and imaginary part (μ ") of complex permeability of the above-described porous iron-cobalt alloy of example 1-fleshy to reveal the mechanism of excellent wave-absorbing performance (μ r =μ' -j μ"). The presence of a plurality of vortex domains in the succulent iron-cobalt alloy, which is a certain improvement in μ' compared to the example 2-spherical porous iron-cobalt alloy, indicates an improvement in magnetic storage capacity. Under alternating magnetic field, magnetic moment near domain wall vibrates more violently and connects with surrounding vortex domain, and μ″ value and magnetic loss capability are improved.
FIG. 4 shows the complex permittivity real part (. Epsilon. ') and permittivity imaginary part (. Epsilon.') of the porous Fe-Co alloy of the above example 1-fleshy to reveal the mechanism of excellent wave-absorbing performance (. Epsilon r =ε '-j. Epsilon.'). The wave absorbing properties of the material are mainly derived from the conductivity loss and polarization loss capabilities. Compared with the porous Fe-Co alloy of example 2-spherically, under the same packing ratio, the connection between samples in the paraffin matrix is reduced due to the volume increase of single fleshy particles, and epsilon' of the fleshy Fe-Co alloy is reduced to a certain extent, so that better impedance matching is realized, and the wave absorbing performance of the fleshy porous Fe-Co alloy is improved.
FIG. 5 shows the reflection loss values in the frequency range of 2.0-18.0GHz at a thickness of 2.0mm for examples 1-4 described above. As shown in the figure, when the thickness of the sample is 2.0mm, the maximum reflection loss value of the fleshy porous iron-cobalt alloy reaches 53.8dB, and the effective absorption bandwidth is 5.7GHz. Example 2-spherical porous ferrocobalt alloy with a maximum reflection loss value of-16.4 dB and an effective absorption bandwidth of 3.6GHz when the thickness of the sample is 2.0 mm; example 3-near fleshy iron-cobalt alloy the maximum reflection loss value reaches-23.8 dB when the sample thickness is 2.0mm, and the effective absorption bandwidth is 5.1GHz; example 4-too much meat-like iron-cobalt alloy at a sample thickness of 2.0mm, the maximum reflection loss value reached-13.5 dB and the effective absorption bandwidth was 2.6GHz. At the same thickness, the microwave absorption performance of examples 2-4 is inferior to that of the porous Fe-Co alloy with fleshy shape of example 1, which shows that the hydrothermal reaction time is an important condition for regulating electromagnetic parameters and further affecting the wave absorption performance. The multi-meat porous iron-cobalt alloy with the micrometer scale meets the practical application requirements of strong absorption, broadband response and thin thickness at the same time, and is a potential high-efficiency wave-absorbing material.
Example 5:
compared to example 1, the vast majority are identical, except in this example:
The molar ratio of the addition amount of the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate, the ammonium fluoride and the urea is 3:1:8:15, and the concentration of Fe 3+ is 0.06mol/L.
Example 6:
compared to example 1, the vast majority are identical, except in this example:
The molar ratio of the addition amount of the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate, the ammonium fluoride and the urea is 1:1:8:15, the concentration of Fe 3+ is 0.02mol/L.
Example 7:
compared to example 1, the vast majority are identical, except in this example:
The molar ratio of the addition amount of the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate, the ammonium fluoride and the urea is 1:1:4:15, the concentration of Fe 3+ is 0.02mol/L.
Example 8:
compared to example 1, the vast majority are identical, except in this example:
the molar ratio of the addition amount of the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate, the ammonium fluoride and the urea is 2:4:10:15.
Example 9:
Most of the same as in example 1, except that in this example, the temperature of the hydrothermal reaction was adjusted to 140 ℃.
Example 10:
most of the same as in example 1, except that in this example, the temperature of the hydrothermal reaction was adjusted to 80 ℃.
Example 11:
most of the same as in example 1 except that in this example, the temperature of the high temperature reduction was adjusted to calcine at 550℃for 3 hours.
Example 12:
Most of the same as in example 1 except that in this example, the temperature of the high temperature reduction was adjusted to calcine at 650 ℃ for 1h.
Example 13:
Most of them are the same as in example 1 except that in this example, the hydrogen gas in the hydrogen argon atmosphere was used in an amount of 4% by volume.
Example 14:
Most of them are the same as in example 1 except that in this example, the volume fraction of hydrogen in the hydrogen argon atmosphere used was 6%.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (4)
1. The preparation method of the micron-scale fleshy porous iron-cobalt alloy is characterized by comprising the following steps of:
(1) Adding ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ammonium fluoride and urea into deionized water, stirring and dissolving to obtain a transparent light pink mixed solution;
(2) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction, washing and drying the obtained reaction product to obtain orange precursor powder;
(3) Placing the precursor powder in hydrogen argon atmosphere for high-temperature reduction, and then cooling to room temperature to obtain a target product;
in the step (1), the mole ratio of ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ammonium fluoride and urea is (1-3): (1-4): (4-10): (12-18);
in the step (1), the addition amount of deionized water satisfies the following conditions: the concentration of Fe 3+ in the mixed solution is 0.01-0.03 mol/L;
In the step (2), the temperature of the hydrothermal reaction is 80-140 ℃ and the time is 40-80 min;
In the step (3), the high-temperature reduction process specifically comprises the following steps: calcining for 1-3 hours at 550-650 ℃;
The prepared porous iron-cobalt alloy is fleshy, has the size of 2-3 mu m, and has a nano-pore structure distributed on the surface, and is used as a microwave absorbing material.
2. The method for preparing the micron-scale fleshy porous iron-cobalt alloy according to claim 1, wherein in the step (2), the washing process is as follows: centrifugal washing with deionized water and ethanol at 8000-10000 rpm deg.C for several times.
3. The method for preparing the micron-scale fleshy porous iron-cobalt alloy according to claim 1, wherein in the step (2), the drying process is specifically as follows: and (5) drying in vacuum at 60-80 ℃.
4. The method for preparing a micrometer-scale fleshy porous iron-cobalt alloy according to claim 1, wherein in the step (3), the volume fraction of hydrogen in the hydrogen-argon atmosphere is 4-6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111576060.4A CN114433860B (en) | 2021-12-22 | 2021-12-22 | Micron-scale fleshy porous iron-cobalt alloy and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111576060.4A CN114433860B (en) | 2021-12-22 | 2021-12-22 | Micron-scale fleshy porous iron-cobalt alloy and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114433860A CN114433860A (en) | 2022-05-06 |
| CN114433860B true CN114433860B (en) | 2024-05-31 |
Family
ID=81364332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111576060.4A Active CN114433860B (en) | 2021-12-22 | 2021-12-22 | Micron-scale fleshy porous iron-cobalt alloy and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114433860B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013185222A (en) * | 2012-03-08 | 2013-09-19 | Japan Science & Technology Agency | bcc TYPE FeCo ALLOY PARTICLE AND MANUFACTURING METHOD THEREOF, AND MAGNET |
| CN104874807A (en) * | 2015-06-17 | 2015-09-02 | 北京科技大学 | Preparation method for nanometer iron-cobalt solid solution alloy powder with body-centered cubic structure |
| CN106917106A (en) * | 2017-01-18 | 2017-07-04 | 北京化工大学 | A kind of preparation method by hydrotalcite topology Synthesis super thin metal alloy nano chip arrays material |
| CN107086314A (en) * | 2017-06-09 | 2017-08-22 | 南京师范大学 | A kind of preparation method of two-dimentional porous noble metal base nano-catalyst |
| CN107902654A (en) * | 2017-10-23 | 2018-04-13 | 东华大学 | A kind of coal tar asphalt is modified the preparation method and application of high-ratio surface porous carbon |
| CN110743555A (en) * | 2019-10-08 | 2020-02-04 | 中国科学院兰州化学物理研究所 | Preparation method of nano porous metal nickel catalyst |
| CN112058282A (en) * | 2019-06-11 | 2020-12-11 | 湖南师范大学 | Preparation method of pH-wide-range catalyst based on molybdenum-tungsten-based layered material and application of pH-wide-range catalyst to electrolytic water-evolution hydrogen reaction |
| CN113078328A (en) * | 2021-03-17 | 2021-07-06 | 浙江大学 | Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821568A (en) * | 2019-03-22 | 2019-05-31 | 大连大学 | A kind of system with molecular sieve for preparing hydrogen catalyst and its preparation method and application |
| US11471873B2 (en) * | 2019-07-24 | 2022-10-18 | Toyota Motor Engineering & Manufacturing North America, Inc. | Microwave synthesis of iron oxide catalysts for cold start NOx removal |
-
2021
- 2021-12-22 CN CN202111576060.4A patent/CN114433860B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013185222A (en) * | 2012-03-08 | 2013-09-19 | Japan Science & Technology Agency | bcc TYPE FeCo ALLOY PARTICLE AND MANUFACTURING METHOD THEREOF, AND MAGNET |
| CN104874807A (en) * | 2015-06-17 | 2015-09-02 | 北京科技大学 | Preparation method for nanometer iron-cobalt solid solution alloy powder with body-centered cubic structure |
| CN106917106A (en) * | 2017-01-18 | 2017-07-04 | 北京化工大学 | A kind of preparation method by hydrotalcite topology Synthesis super thin metal alloy nano chip arrays material |
| CN107086314A (en) * | 2017-06-09 | 2017-08-22 | 南京师范大学 | A kind of preparation method of two-dimentional porous noble metal base nano-catalyst |
| CN107902654A (en) * | 2017-10-23 | 2018-04-13 | 东华大学 | A kind of coal tar asphalt is modified the preparation method and application of high-ratio surface porous carbon |
| CN112058282A (en) * | 2019-06-11 | 2020-12-11 | 湖南师范大学 | Preparation method of pH-wide-range catalyst based on molybdenum-tungsten-based layered material and application of pH-wide-range catalyst to electrolytic water-evolution hydrogen reaction |
| CN110743555A (en) * | 2019-10-08 | 2020-02-04 | 中国科学院兰州化学物理研究所 | Preparation method of nano porous metal nickel catalyst |
| CN113078328A (en) * | 2021-03-17 | 2021-07-06 | 浙江大学 | Co-FPOH microsphere material for water system zinc-air battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114433860A (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108154984B (en) | Porous ferroferric oxide/carbon nano rod-shaped electromagnetic wave absorption material and preparation method and application thereof | |
| CN110283570B (en) | FeCo @ MXene core-shell structure composite wave-absorbing material and preparation method thereof | |
| CN107033842B (en) | A kind of composite wave-absorbing agent, preparation method and applications | |
| CN111392771A (en) | Core-shell structure nitrogen-doped carbon-coated titanium dioxide microsphere composite material with controllable shell morphology and preparation and application thereof | |
| CN112251193A (en) | Composite wave-absorbing material based on MXene and metal organic framework and preparation method and application thereof | |
| CN110790316B (en) | Iron oxide-nitrogen doped carbon micron tube composite wave-absorbing material and preparation method thereof | |
| CN112047386A (en) | Heating modified MXene/ferroferric oxide composite wave-absorbing material and preparation method thereof | |
| CN112743098B (en) | Preparation method of nitrogen-doped porous carbon-coated hollow cobalt-nickel alloy composite wave-absorbing material | |
| Liang et al. | Fe-MOFs derived porous Fe4N@ carbon composites with excellent broadband electromagnetic wave absorption properties | |
| CN101521046B (en) | Graphite sheet surface load magnetic alloy particle wave-absorbing material and preparation method thereof | |
| CN109896520A (en) | A kind of magnetizing reduction stannic oxide/graphene nano composite material and preparation method and application | |
| CN110437800A (en) | ZrO derived from a kind of Co modified metal organic frame2/ C electromagnetic wave absorbent material and the preparation method and application thereof | |
| CN114449877A (en) | Core-shell Ni/Co alloy @ nitrogen-doped carbon-based wave-absorbing composite material and preparation method thereof | |
| CN110669228B (en) | CoFe/C composite material and preparation method and application thereof | |
| CN112537764A (en) | Carbon-based porous composite wave absorbing agent based on natural loofah sponge and preparation method thereof | |
| Liang et al. | Electromagnetic response and microwave absorption properties of CF/Fe3O4 absorbing composites | |
| CN109699165B (en) | Three-dimensional porous manganese oxide-cobalt composite electromagnetic wave absorption material and preparation method and application thereof | |
| CN114433860B (en) | Micron-scale fleshy porous iron-cobalt alloy and preparation and application thereof | |
| Qin et al. | Enhance the electromagnetic absorption performance of Co&Ni@ GNs by designing appropriate cCo: cNi deposited on GNs surface | |
| CN110340376B (en) | Flower-shaped nickel wire wave-absorbing material and preparation method thereof | |
| CN113708085B (en) | Preparation method of nano porous carbon coated magnetic nanoparticle compound | |
| CN114073919B (en) | Carbon-magnetic metal dispersion type hollow composite microsphere and preparation method and application thereof | |
| CN115028847A (en) | CoNi alloy MOF porous material and preparation and application thereof | |
| CN114411132A (en) | Preparation method of cobalt-nickel alloy particle hydrophilic carbon cloth composite material with corn cob-like heterostructure | |
| CN116322007B (en) | NiFe-CNTs-RGO composite aerogel material with three-dimensional interconnected pore structure, and preparation method and application thereof |
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 |