CN117550645A - Preparation process and application of manganese zinc ferrite superfine powder - Google Patents
Preparation process and application of manganese zinc ferrite superfine powder Download PDFInfo
- Publication number
- CN117550645A CN117550645A CN202311446776.1A CN202311446776A CN117550645A CN 117550645 A CN117550645 A CN 117550645A CN 202311446776 A CN202311446776 A CN 202311446776A CN 117550645 A CN117550645 A CN 117550645A
- Authority
- CN
- China
- Prior art keywords
- manganese
- zinc
- zinc ferrite
- superfine powder
- ferrite
- 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.)
- Pending
Links
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000000843 powder Substances 0.000 title claims abstract description 78
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011358 absorbing material Substances 0.000 claims abstract description 27
- 239000011787 zinc oxide Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 15
- 239000001099 ammonium carbonate Substances 0.000 claims description 15
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 239000002071 nanotube Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 9
- 229960001763 zinc sulfate Drugs 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000006185 dispersion Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002041 carbon nanotube Substances 0.000 abstract description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000010287 polarization Effects 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 3
- 239000006249 magnetic particle Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000005476 size effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract 1
- 230000003746 surface roughness Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LNRYQGINUXUWLV-UHFFFAOYSA-N [Mn].[Fe].[Zn] Chemical compound [Mn].[Fe].[Zn] LNRYQGINUXUWLV-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
- H01Q17/004—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems using non-directional dissipative particles, e.g. ferrite powders
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Abstract
The invention relates to the technical field of manganese zinc ferrite, and discloses a preparation process and application of manganese zinc ferrite superfine powder, wherein cavitation and impact of ultrasonic waves improve the generation rate of crystal nuclei in the precipitation process, so that the prepared manganese zinc ferrite superfine powder has fine particle size; the porous spherical zinc oxide has quantum size effect and antenna-like structure, and charges are accumulated at the needle point to form a plurality of polarization centers, so that the electromagnetic waves are scattered and reflected; the carbon nano tube cavity is fine and long, has strong capillary action and can absorb magnetic particles to generate magnetic loss; the nano particle size of the modified manganese zinc ferrite superfine powder increases the surface roughness of the material, meanwhile, the surface atoms lack coordination, the dangling bonds are increased, and the interface polarization and multiple scattering are beneficial to the attenuation of microwaves; the invention combines the wave-absorbing characteristics of the three materials to prepare the wave-absorbing material with wide absorption band, good compatibility, light weight and thin thickness.
Description
Technical Field
The invention relates to the technical field of manganese-zinc ferrite, in particular to a preparation process and application of manganese-zinc ferrite superfine powder.
Background
Manganese zinc ferrite materials are widely applied to the fields of electronic information and military due to the advantages of high resistivity, small loss, good dielectric property and the like, along with the development of continuous microminiaturization, thinning and high performance of electronic devices, manganese zinc ferrite ultrafine powder has excellent nano-size characteristics and potential application value, and gradually replaces the traditional metal magnetic materials to become the focus of attention, in recent years, research on manganese zinc ferrite ultrafine powder is carried out in the process of heating, for example, the manganese zinc ferrite ultrafine powder is prepared in the prior art, a solid phase method and a coprecipitation method are applied more, but the problems are that the powder prepared by the solid phase method is low in purity, poor in uniformity, easy to generate agglomeration, large in particle size and high in reaction temperature are needed; the precipitate obtained by the traditional coprecipitation reaction is difficult to wash and filter in a colloid state, and even each component can be segregated, especially for a ferrite of a multicomponent system, the coprecipitation is slow, and the process has long turnover time.
Electromagnetic pollution becomes the fourth pollution after air pollution, water pollution and noise pollution, wave absorbing materials capable of effectively resisting and weakening electromagnetic radiation become research hot spots of novel functional materials, manganese-zinc ferrite has excellent magnetic performance, and is widely applied in the field of electromagnetic wave absorbing materials, but single ferrite materials can not meet the current use requirements, ferrite as a traditional wave absorbing material has the defects of large density, narrow absorption band and the like and is not suitable for practical application, so that the nano ferrite composite material provides a new way for developing high-performance new materials and improving the performance of the existing materials and becomes an important direction for new material research.
Due to the special structure and dielectric property of the carbon nanotube, the wave absorbing performance of the composite material synthesized by the carbon nanotube and other materials has shown good application prospect, and some nano materials have excellent wave absorbing characteristics, quantum size effect, tunnel effect and the like, for example, nano zinc oxide can be used as the wave absorbing material, so that radar detection can be avoided in a very wide frequency band range, and the composite material has the characteristics of good compatibility, small quality, thin thickness and the like; according to the invention, the manganese-zinc ferrite superfine powder is prepared by adopting an ultrasonic coprecipitation method, the surface of the manganese-zinc ferrite superfine powder is modified, and the obtained modified manganese-zinc ferrite superfine powder is blended with porous spherical zinc oxide and carbon oxide nanotubes to obtain the composite wave-absorbing material with excellent performance, so that the process is simple and the implementation is convenient.
Disclosure of Invention
The invention solves the technical problems that: provides a preparation process and application of manganese zinc ferrite superfine powder, solves the problem that the superfine powder prepared by the traditional method is easy to agglomerate, and prepares the composite wave-absorbing material with excellent comprehensive performance.
The technical scheme of the invention is as follows:
the preparation process of the manganese zinc ferrite superfine powder comprises the following steps:
(1) FeCl was added to the reaction flask 3 ，MnCl 2 ，ZnCl 2 And deionized water, stirring and dispersing, adding dispersant oleic acid under the protection of nitrogen, stirring at 40-60 ℃ for 10-30min, adding ammonia water to control the pH of the system to be 7-9, then dripping coprecipitation agent, stirring and dispersing, placing the mixed solution in an ultrasonic generator for ultrasonic auxiliary reaction, filtering after the reaction is finished, washing a filter cake by ethanol and deionized water, and drying to obtain the manganese zinc ferrite precursor.
(2) Adding the manganese-zinc ferrite precursor into a high-temperature furnace, heating the high-temperature furnace to 350-500 ℃ at the speed of 3-5 ℃/min, preserving heat for 1-2h, preserving heat for 2-4h at 800-900 ℃, and naturally cooling to obtain manganese-zinc ferrite superfine powder.
Further, feCl in the step (1) 3 、MnCl 2 、ZnCl 2 The proportions of oleic acid and coprecipitate are as follows: 4mol:1 mol:0.1-0.35mol:0.01-0.03mol.
Further, the coprecipitation agent in the step (1) is any one of ammonium oxalate or ammonium bicarbonate.
Further, in the step (1), the power of the ultrasonic generator is 50-300W, the ultrasonic auxiliary temperature is 30-45 ℃ and the time is 10-50min.
And S1, adding a mixed solvent of manganese zinc ferrite superfine powder, ethanol and deionized water into a reaction bottle, uniformly stirring, adding KH550, stirring for reaction, filtering after the reaction is finished, washing with acetone and deionized water, and drying to obtain the modified manganese zinc ferrite superfine powder.
S2, adding zinc sulfate, ammonium carbonate and deionized water into a reaction bottle, stirring uniformly at room temperature, adding a dispersing agent polyethylene glycol, stirring at 20-35 ℃ for 8-16h, then placing the mixed solution into a tube furnace, heating to 400-500 ℃ at a heating rate of 4-8 ℃/min under a nitrogen atmosphere, reacting at constant temperature for 5-10h, and naturally cooling to obtain the porous spherical zinc oxide.
S3, adding the modified manganese zinc ferrite superfine powder, the porous spherical zinc oxide and the ethanol into a reaction bottle, stirring and dispersing, adding the carbon oxide nano tube, performing ultrasonic dispersion for 20-40min at 20-35 ℃, performing deionized washing, and drying to obtain the manganese zinc ferrite superfine powder wave-absorbing material.
Further, in the step S1, the proportion of the manganese zinc ferrite superfine powder to the KH550 is as follows: 1g of the powder is 0.5-1g.
Further, the reaction temperature in the step S1 is 60-80 ℃ and the reaction time is 4-8h.
Further, in the step S2, the ratio of zinc sulfate, ammonium carbonate and polyethylene glycol is: 1mol:1-3mol:15-25g.
Further, the proportion of the modified manganese zinc ferrite superfine powder, the porous spherical zinc oxide and the carbon oxide nano tube in the step S3 is as follows: 1g to 5g and 0.05 g to 0.25g.
The beneficial technical effects of the invention are as follows:
the invention uses FeCl 3 ，MnCl 2 ，ZnCl 2 And dispersant oleic acid, coprecipitation agent ammonium oxalate or ammonium bicarbonate are subjected to coprecipitation reaction in an ultrasonic generator, manganese zinc ferrite precursors are obtained by controlling ultrasonic frequency, and the manganese zinc ferrite precursors are calcined at high temperature to obtain manganese zinc iron with nanometer particle sizeOxygen ultra-fine powder; KH550 is adopted to modify the surface of the manganese zinc ferrite superfine powder, so that powder agglomeration is avoided, then zinc sulfate, ammonium carbonate and dispersant polyethylene glycol are utilized to react in a reaction kettle to obtain porous spherical zinc oxide, and finally the modified manganese zinc ferrite superfine powder, the porous spherical zinc oxide and the carbon oxide nano tube are blended to obtain the manganese zinc ferrite superfine powder wave absorbing material.
The manganese zinc ferrite superfine powder prepared by adopting an ultrasonic coprecipitation method has the function of improving the dispersibility and the particle size distribution of the nano particles; the cavitation effect and the impact effect of ultrasonic waves are utilized, crystal grains are crushed, precipitated and refined, the generation rate of crystal nuclei in the precipitation process is improved, a large number of bubbles can be generated in the ultrasonic auxiliary process, and the bubbles can be attached to the surface of the precipitate to reduce the surface energy of the precipitate, so that the aggregation of the crystal nuclei becomes more difficult, and the particle size of the prepared material is smaller.
The porous spherical zinc oxide has quantum size effect and antenna-like structure, charges are accumulated at the needle point to form a plurality of polarization centers, so that the electromagnetic waves are scattered and reflected, and the microwave absorption capacity is enhanced; the carbon nano tube cavity is fine and long, has strong capillary action, can suck magnetic particles into the tube cavity and is densely arranged, and generates certain magnetic loss, so that the microwave absorption performance is realized; the modified manganese zinc ferrite superfine powder has larger specific surface area and nano size, the roughness of the surface of the material is increased due to the reduction of the particle size, the attenuation of microwaves is facilitated, meanwhile, the surface atoms lack coordination, and the suspension bonds are increased, so that interface polarization and multiple scattering become important wave absorbing channels; the three components are compounded to produce a synergistic wave-absorbing effect, so that the wave-absorbing performance of the material is improved, and the characteristics of the wave-absorbing material, such as required absorption bandwidth, good compatibility, light weight and thin thickness, are met.
Description of the embodiments
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation of oxidized carbon nanotubes: weighing 5g of carbon nano tube, calcining for 2 hours at 520 ℃, adding the carbon nano tube into a mixed solution of 100mL of concentrated sulfuric acid and 10mL of concentrated nitric acid, performing ultrasonic dispersion for 30 minutes, stirring for 2 hours at 80 ℃, cooling, adding 600mL of deionized water for dilution, standing for 6 hours at room temperature, filtering, washing with deionized water, and drying to obtain the carbon oxide nano tube.
Preparation of manganese zinc ferrite superfine powder:
(1) 4mol of FeCl was added to the reaction flask 3 1mol of MnCl 2 1mol of ZnCl 2 And deionized water, stirring and dispersing, adding 0.1-0.35mol of dispersant oleic acid under the protection of nitrogen, stirring for 10-30min at 40-60 ℃, adding ammonia water to control the pH of the system to be 7-9, then dropwise adding 0.01-0.03mol of coprecipitator ammonium oxalate or ammonium bicarbonate, stirring and dispersing, placing the mixed solution in a 50-300W ultrasonic generator, performing ultrasonic assistance for 10-50min at 30-45 ℃, filtering, washing a filter cake with ethanol and deionized water, and drying to obtain the manganese zinc ferrite precursor.
(2) Adding the manganese-zinc ferrite precursor into a high-temperature furnace, heating the high-temperature furnace to 350-500 ℃ at the speed of 3-5 ℃/min, preserving heat for 1-2h, preserving heat for 2-4h at 800-900 ℃, and naturally cooling to obtain manganese-zinc ferrite superfine powder.
Preparation of manganese zinc ferrite superfine powder wave-absorbing material:
s1, adding 1g of mixed solvent of manganese zinc ferrite superfine powder, ethanol and deionized water into a reaction bottle, uniformly stirring, adding 0.5-1g of KH550, stirring for reaction, reacting at 60-80 ℃ for 4-8h, filtering, washing with acetone and deionized water, and drying to obtain the modified manganese zinc ferrite superfine powder.
S2, adding 1mol of zinc sulfate, 1-3mol of ammonium carbonate and deionized water into a reaction bottle, uniformly stirring at room temperature, adding 15-25g of dispersing agent polyethylene glycol, stirring at 20-35 ℃ for 8-16h, then placing the mixed solution into a tube furnace, heating to 400-500 ℃ at a heating rate of 4-8 ℃/min under nitrogen atmosphere, reacting at constant temperature for 5-10h, and naturally cooling to obtain the porous spherical zinc oxide.
S3, adding 1g of modified manganese zinc ferrite superfine powder, 1-5g of porous spherical zinc oxide and ethanol into a reaction bottle, stirring and dispersing, adding 0.05-0.25g of carbon oxide nano tube, performing ultrasonic dispersion for 20-40min at 20-35 ℃, performing deionized washing, and drying to obtain the manganese zinc ferrite superfine powder wave-absorbing material.
Examples
(1) Into a reaction flask was charged 10mmol of FeCl 3 2.5mmol of MnCl 2 ZnCl 2.5mmol 2 And deionized water, stirring and dispersing, adding 2.8mmol of dispersant oleic acid under the protection of nitrogen, stirring at 55 ℃ for 15min, adding ammonia water to control the pH of the system to be 7, then dropwise adding 0.2mmol of coprecipitator ammonium bicarbonate, stirring and dispersing, placing the mixed solution in a 50W ultrasonic generator, performing ultrasonic assistance at 40 ℃ for 20min, filtering, washing a filter cake with ethanol and deionized water, and drying to obtain the manganese zinc ferrite precursor.
(2) Adding the manganese-zinc ferrite precursor into a high-temperature furnace, heating the high-temperature furnace to 450 ℃ at the speed of 4 ℃/min, preserving heat for 1h, preserving heat for 4h at 800 ℃, and naturally cooling to obtain manganese-zinc ferrite superfine powder.
Examples
(1) 2mmol of FeCl was added to the reaction flask 3 0.5mmol MnCl 2 ZnCl of 0.5mmol 2 And deionized water, stirring and dispersing, adding 0.1mmol of dispersant oleic acid under the protection of nitrogen, stirring at 50 ℃ for 20min, adding ammonia water to control the pH of the system to be 8, then dropwise adding 0.015mmol of coprecipitate ammonium oxalate, stirring and dispersing, placing the mixed solution in a 130W ultrasonic generator, performing ultrasonic assistance at 30 ℃ for 15min, filtering, washing a filter cake with ethanol and deionized water, and drying to obtain the manganese zinc ferrite precursor.
(2) Adding the manganese-zinc ferrite precursor into a high-temperature furnace, heating the high-temperature furnace to 450 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, preserving heat for 3 hours at 850 ℃, and naturally cooling to obtain manganese-zinc ferrite superfine powder.
Examples
(1) Into a reaction flask was charged 4mmol of FeCl 3 1mmol of MnCl 2 1mmol of ZnCl 2 And deionized waterStirring and dispersing, adding 0.35mmol of dispersant oleic acid under the protection of nitrogen, stirring at 60 ℃ for 30min, adding ammonia water to control the pH of the system to be 9, then dropwise adding 0.03mmol of coprecipitator ammonium bicarbonate, stirring and dispersing, placing the mixed solution in a 210W ultrasonic generator, performing ultrasonic assistance at 35 ℃ for 30min, filtering, washing a filter cake with ethanol and deionized water, and drying to obtain the manganese zinc ferrite precursor.
(2) Adding the manganese-zinc ferrite precursor into a high-temperature furnace, heating the high-temperature furnace to 350 ℃ at the speed of 3 ℃/min, preserving heat for 2 hours, preserving heat for 4 hours at 900 ℃, and naturally cooling to obtain manganese-zinc ferrite superfine powder.
Examples
(1) Into a reaction flask was charged 8mmol of FeCl 3 2mmol of MnCl 2 ZnCl of 2mmol 2 And deionized water, stirring and dispersing, adding 0.2mmol of dispersant oleic acid under the protection of nitrogen, stirring at 40 ℃ for 10min, adding ammonia water to control the pH of the system to be 9, then dropwise adding 0.02mmol of coprecipitator ammonium oxalate, stirring and dispersing, placing the mixed solution into a 300W ultrasonic generator, performing ultrasonic assistance at 35 ℃ for 40min, filtering, washing a filter cake with ethanol and deionized water, and drying to obtain the manganese zinc ferrite precursor.
(2) Adding the manganese-zinc ferrite precursor into a high-temperature furnace, heating the high-temperature furnace to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, preserving heat for 3 hours at 900 ℃, and naturally cooling to obtain manganese-zinc ferrite superfine powder.
Particle size testing: powder particle size testing was performed using a laser particle sizer.
Magnetic performance test: the saturation magnetization of the sample was tested using a vibrating sample magnetometer.
| Average particle diameter (nm) | Saturation magnetization (emu/g) | |
| Example 1 | 20.02 | 73.03 |
| Example 2 | 10.35 | 74.94 |
| Example 3 | 11.21 | 77.45 |
| Example 4 | 11.58 | 76.72 |
As shown by the test results of the table, the granularity of the Mn-Zn ferrite is gradually reduced along with the increase of the ultrasonic power, and the average grain diameter is 10.35nm when the ultrasonic power of the embodiment 2 is 130W, which indicates that the superfine powder prepared by combining the ultrasonic method with the coprecipitation method has fine grain diameter and meets the requirement of nano particles; the method is characterized in that the impact effect and cavitation effect of ultrasonic waves can crush precipitated refined grains, so that the generation rate of crystal nuclei in the precipitation process is greatly improved, and the particle size of the precipitate is smaller; in addition, a large amount of bubbles can be generated in the ultrasonic auxiliary process, and the bubbles can be attached to the surface of the sediment so as to reduce the surface energy of the sediment, so that the aggregation of crystal nucleus becomes more difficult, and the aggregation phenomenon of particles is reduced; the average particle diameter of example 3 was 11.21nm, the saturation magnetization was 77.45emu/g, and the overall properties were excellent, so that the subsequent sample preparation was carried out with a microwave power of 210W.
Examples
S1, adding 2g of manganese zinc ferrite superfine powder (prepared in example 3), 200mL of ethanol and 200mL of deionized water into a reaction bottle, uniformly stirring, adding 3g of KH550, stirring for reaction, reacting at 70 ℃ for 5 hours, filtering, washing with acetone and deionized water, and drying to obtain the modified manganese zinc ferrite superfine powder.
S2, adding 1mmol of zinc sulfate, 2mmol of ammonium carbonate and deionized water into a reaction bottle, uniformly stirring at room temperature, adding 0.02g of dispersing agent polyethylene glycol, stirring at 25 ℃ for 12 hours, then placing the mixed solution into a tube furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, reacting at constant temperature for 8 hours, and naturally cooling to obtain the porous spherical zinc oxide.
S3, adding 1g of modified manganese zinc ferrite superfine powder, 2g of porous spherical zinc oxide and ethanol into a reaction bottle, stirring and dispersing, adding 0.2g of carbon oxide nano tube, performing ultrasonic dispersion for 30min at 30 ℃, performing deionized washing, and drying to obtain the manganese zinc ferrite superfine powder wave-absorbing material.
Examples
S1, adding 5g of manganese zinc ferrite superfine powder (prepared in example 3), 500mL of mixed solvent of ethanol and 500mL of deionized water into a reaction bottle, uniformly stirring, adding 4.5g of KH550, stirring for reaction, reacting at 80 ℃ for 4 hours, filtering, washing with acetone and deionized water, and drying to obtain the modified manganese zinc ferrite superfine powder.
S2, adding 3mmol of zinc sulfate, 8mmol of ammonium carbonate and deionized water into a reaction bottle, uniformly stirring at room temperature, adding 0.06g of dispersing agent polyethylene glycol, stirring at 20 ℃ for 16 hours, then placing the mixed solution into a tube furnace, heating to 500 ℃ at a heating rate of 8 ℃/min under a nitrogen atmosphere, reacting at constant temperature for 10 hours, and naturally cooling to obtain the porous spherical zinc oxide.
S3, adding 1g of modified manganese zinc ferrite superfine powder, 3g of porous spherical zinc oxide and ethanol into a reaction bottle, stirring and dispersing, adding 0.15g of carbon oxide nano tube, performing ultrasonic dispersion at 25 ℃ for 40min, performing deionized washing, and drying to obtain the manganese zinc ferrite superfine powder wave-absorbing material.
Examples
S1, adding 10g of manganese zinc ferrite superfine powder (prepared in example 3), 1000mL of ethanol and 1000mL of deionized water into a reaction bottle, uniformly stirring, adding 8g of KH550, stirring for reaction, reacting at 65 ℃ for 8 hours, filtering, washing with acetone and deionized water, and drying to obtain the modified manganese zinc ferrite superfine powder.
S2, adding 1mmol of zinc sulfate, 3mmol of ammonium carbonate and deionized water into a reaction bottle, uniformly stirring at room temperature, adding 0.025g of dispersing agent polyethylene glycol, stirring at 35 ℃ for 15 hours, then placing the mixed solution into a tube furnace, heating to 400 ℃ at a heating rate of 6 ℃/min under a nitrogen atmosphere, reacting at constant temperature for 6 hours, and naturally cooling to obtain the porous spherical zinc oxide.
S3, adding 1g of modified manganese zinc ferrite superfine powder, 4g of porous spherical zinc oxide and ethanol into a reaction bottle, stirring and dispersing, adding 0.1g of carbon oxide nano tube, performing ultrasonic dispersion at 30 ℃ for 35min, performing deionized washing, and drying to obtain the manganese zinc ferrite superfine powder wave-absorbing material.
Comparative example 1
Adding 2g of porous spherical zinc oxide and ethanol into a reaction bottle, stirring and dispersing, adding 0.2g of carbon oxide nano tube, performing ultrasonic dispersion for 30min at 30 ℃, performing deionized washing, and drying to obtain the wave-absorbing material.
Comparative example 2
Adding 1g of modified manganese zinc ferrite superfine powder and ethanol into a reaction bottle, stirring and dispersing, adding 0.2g of carbon oxide nano tube, performing ultrasonic dispersion for 30min at 30 ℃, performing deionized washing, and drying to obtain the wave-absorbing material.
Comparative example 3
Adding 1g of modified manganese zinc ferrite superfine powder, 2g of porous spherical zinc oxide and ethanol into a reaction bottle, performing ultrasonic dispersion at 30 ℃ for 30min, performing deionized washing, and drying to obtain the wave-absorbing material.
Comparative example 4
This comparative example consists of porous spherical zinc oxide prepared in example 5 alone to form a wave-absorbing material.
Comparative example 5
The comparative example consisted of carbon oxide nanotubes alone to form the wave-absorbing material.
Comparative example 6
The comparative example consists of modified manganese zinc ferrite superfine powder prepared in the example 5 and the wave-absorbing material.
Wave absorbing performance test: the samples prepared in examples 5-7 and comparative examples 1-6 were respectively prepared with paraffin wax in a mass ratio of 7:3 to prepare annular samples to be tested having an outer diameter of 10mm, an inner diameter of 5mm and a height of 2mm, and the wave absorbing performance of the materials in the frequency range of 2-18GHz was tested by using a network analyzer.
| Maximum value of reflection loss (dB) | Less than or equal to-10 dB bandwidth (GHz) | |
| Example 5 | -32.3 | 3.8 |
| Example 6 | -41.1 | 4.5 |
| Example 7 | -46.5 | 4.1 |
| Comparative example 1 | -24.1 | 2.6 |
| Comparative example 2 | -19.4 | 2.5 |
| Comparative example 3 | -16.0 | 2.0 |
| Comparative example 4 | -7.7 | 1.4 |
| Comparative example 5 | -5.6 | 0.9 |
| Comparative example 6 | -10.1 | 1.7 |
The reflection loss refers to the proportion of the energy lost when the electromagnetic wave is reflected on the surface of the material to the incident energy, and the smaller the reflection loss is, the stronger the absorption capacity of the material to the electromagnetic wave is. As shown by the test data in the table, the reflection loss value of the embodiment 5-7 is in the range of-32.3 to-46.5 dB, and the wave absorbing performance is better, because the modified manganese zinc ferrite superfine powder, the porous spherical zinc oxide and the carbon oxide nano tube all have the wave absorbing performance: the modified manganese zinc ferrite superfine powder has larger specific surface area and nano size, the roughness of the surface of the material is increased due to the reduction of the particle size, the attenuation of microwaves is facilitated, meanwhile, the surface atoms lack coordination, and the suspension bonds are increased, so that interface polarization and multiple scattering become important wave absorbing channels; the pore-spherical zinc oxide has rich pore structures and antenna-like structures, charges are accumulated at the needle point to form a plurality of polarization centers, so that the electromagnetic waves are scattered and reflected, and the microwave receiving capacity is enhanced; the carbon nano tube cavity is fine and long, has strong capillary action, can suck magnetic particles into the tube cavity and is densely arranged, and generates certain magnetic loss, so that the carbon nano tube has microwave absorption performance, and the three components are compounded to generate a synergistic wave absorbing effect.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation process of the manganese zinc ferrite superfine powder is characterized by comprising the following steps of:
(1) FeCl was added to the reaction flask 3 ，MnCl 2 ，ZnCl 2 Adding dispersant oleic acid under the protection of nitrogen, stirring at 40-60 ℃ for 10-30min, adding ammonia water to control the pH of the system to be 7-9, then dripping coprecipitation agent, stirring for dispersion, placing the mixed solution into an ultrasonic generator for ultrasonic auxiliary reaction, filtering after the reaction is finished, washing a filter cake with ethanol and deionized water, and drying to obtain a manganese zinc ferrite precursor;
(2) Adding the manganese-zinc ferrite precursor into a high-temperature furnace, heating the high-temperature furnace to 350-500 ℃ at the speed of 3-5 ℃/min, preserving heat for 1-2h, preserving heat for 2-4h at 800-900 ℃, and naturally cooling to obtain manganese-zinc ferrite superfine powder.
2. The process for preparing manganese-zinc-ferrite ultra-fine powder according to claim 1, wherein FeCl is used in the step (1) 3 、MnCl 2 、ZnCl 2 The proportions of oleic acid and coprecipitate are as follows: 4mol:1 mol:0.1-0.35mol:0.01-0.03mol.
3. The process for preparing manganese-zinc-ferrite ultra-fine powder according to claim 2, wherein the coprecipitator in the step (1) is any one of ammonium oxalate or ammonium bicarbonate.
4. The process for preparing the manganese-zinc-ferrite ultra-fine powder according to claim 1, wherein the power of the ultrasonic generator in the step (1) is 50-300W, the ultrasonic auxiliary temperature is 30-45 ℃ and the time is 10-50min.
5. An application of the manganese-zinc ferrite superfine powder obtained by the preparation process according to any one of claims 1 to 4 in a wave-absorbing material, which is characterized in that:
s1, adding a mixed solvent of manganese zinc ferrite superfine powder, ethanol and deionized water into a reaction bottle, uniformly stirring, adding KH550, stirring for reaction, filtering after the reaction is finished, washing with acetone and deionized water, and drying to obtain modified manganese zinc ferrite superfine powder;
s2, adding zinc sulfate, ammonium carbonate and deionized water into a reaction bottle, stirring uniformly at room temperature, adding a dispersing agent polyethylene glycol, stirring at 20-35 ℃ for 8-16 hours, then placing the mixed solution into a tube furnace, heating to 400-500 ℃ at a heating rate of 4-8 ℃/min under a nitrogen atmosphere, reacting at constant temperature for 5-10 hours, and naturally cooling to obtain porous spherical zinc oxide;
s3, adding the modified manganese zinc ferrite superfine powder, the porous spherical zinc oxide and the ethanol into a reaction bottle, stirring and dispersing, adding the carbon oxide nano tube, performing ultrasonic dispersion for 20-40min at 20-35 ℃, performing deionized washing, and drying to obtain the manganese zinc ferrite superfine powder wave-absorbing material.
6. The application of the manganese-zinc-ferrite ultra-fine powder in the wave-absorbing material according to claim 5, wherein the proportion of the manganese-zinc-ferrite ultra-fine powder to the KH550 in the step S1 is as follows: 1g of the powder is 0.5-1g.
7. The application of the manganese zinc ferrite ultra-fine powder in the wave-absorbing material according to claim 5, wherein the reaction temperature in the step S1 is 60-80 ℃ and the reaction time is 4-8h.
8. The application of the manganese-zinc-ferrite ultra-fine powder in the wave-absorbing material according to claim 5, wherein the proportion of zinc sulfate, ammonium carbonate and polyethylene glycol in the step S2 is as follows: 1mol:1-3mol:15-25g.
9. The application of the manganese-zinc-ferrite ultra-fine powder in the wave-absorbing material according to claim 5, wherein the proportion of the modified manganese-zinc-ferrite ultra-fine powder, the porous spherical zinc oxide and the carbon oxide nano tube in the step S3 is as follows: 1g to 5g and 0.05 g to 0.25g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311446776.1A CN117550645A (en) | 2023-11-02 | 2023-11-02 | Preparation process and application of manganese zinc ferrite superfine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311446776.1A CN117550645A (en) | 2023-11-02 | 2023-11-02 | Preparation process and application of manganese zinc ferrite superfine powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117550645A true CN117550645A (en) | 2024-02-13 |
Family
ID=89813771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311446776.1A Pending CN117550645A (en) | 2023-11-02 | 2023-11-02 | Preparation process and application of manganese zinc ferrite superfine powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117550645A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040183711A1 (en) * | 2003-02-14 | 2004-09-23 | Minebea Co., Ltd. | Electromagnetic wave absorber formed of Mn-Zn ferrite |
| CN1533985A (en) * | 2003-03-31 | 2004-10-06 | 上海大学 | Preparation method of nano-grade zinc oxide powder |
| CN101834044A (en) * | 2009-09-10 | 2010-09-15 | 深圳大学 | Method for preparing manganese zinc ferrite-coated carbon nano tube magnetic material |
| CN102503390A (en) * | 2011-10-20 | 2012-06-20 | 同济大学 | Preparation method of manganese-zinc ferrite magnetic nanoparticle |
| WO2022110626A1 (en) * | 2020-11-30 | 2022-06-02 | 横店集团东磁股份有限公司 | Ferrite material for electromagnetic absorption and shielding, and electromagnetic wave absorber and preparation method therefor |
-
2023
- 2023-11-02 CN CN202311446776.1A patent/CN117550645A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040183711A1 (en) * | 2003-02-14 | 2004-09-23 | Minebea Co., Ltd. | Electromagnetic wave absorber formed of Mn-Zn ferrite |
| CN1533985A (en) * | 2003-03-31 | 2004-10-06 | 上海大学 | Preparation method of nano-grade zinc oxide powder |
| CN101834044A (en) * | 2009-09-10 | 2010-09-15 | 深圳大学 | Method for preparing manganese zinc ferrite-coated carbon nano tube magnetic material |
| CN102503390A (en) * | 2011-10-20 | 2012-06-20 | 同济大学 | Preparation method of manganese-zinc ferrite magnetic nanoparticle |
| WO2022110626A1 (en) * | 2020-11-30 | 2022-06-02 | 横店集团东磁股份有限公司 | Ferrite material for electromagnetic absorption and shielding, and electromagnetic wave absorber and preparation method therefor |
Non-Patent Citations (3)
| Title |
|---|
| A TAUFIQ ET AL.: ""Preparation of Superparamagnetic Zn0.5Mn0.5Fe2O4 Particle by Coprecipitation- Sonochemical Method for Radar Absorbing Material"", 《THE 4TH INTERNATIONAL CONFERENCE ON ADVANCED MATERIALS SCIENCE AND TECHNOLOGY》, vol. 202, 31 December 2017 (2017-12-31), pages 1 - 11 * |
| SWAPNIL VAISH ET AL.: ""STRUCTURAL, OPTICAL AND DIELECTRIC PROPERTIES OF TRANSITION METAL (MFe2O4; M= Co, Ni, Zn) NANOFERRITES"", 《PHYSICA B》, vol. 524, 31 December 2017 (2017-12-31), pages 53 - 63, XP085197990, DOI: 10.1016/j.physb.2017.08.060 * |
| YUPING DUAN ET AL.: "Structure and composition design on ternary CNT@ZnFe2O4@ZnO composite utilized as enhanced microwave absorbing materials"", 《DIAMOND & RELATED MATERIALS》, vol. 120, 31 December 2021 (2021-12-31), pages 108701 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shu et al. | Fabrication of bimetallic metal-organic frameworks derived Fe3O4/C decorated graphene composites as high-efficiency and broadband microwave absorbers | |
| Feng et al. | Synthesis of a hierarchical carbon fiber@ cobalt ferrite@ manganese dioxide composite and its application as a microwave absorber | |
| CN109762519B (en) | Preparation method of high-entropy alloy/oxide composite nano wave-absorbing material | |
| CN108039257B (en) | A kind of three-dimensional porous sheet ferroferric oxide/carbon nano electromagnetic wave absorbing material and preparation method thereof | |
| CN102190332B (en) | Electromagnetic wave absorbing material of monodisperse nanometer ferriferrous oxide hollow ball, its preparation method and application | |
| CN108124413B (en) | Porous hollow iron nanometer spherical electromagnetic wave absorbent material and preparation method and application | |
| CN107949266A (en) | A kind of three-dimensional porous flower-like structure cobalt/carbon nano composite electromagnetic wave absorption material and preparation method thereof | |
| CN101299914A (en) | Nanocrystalline ultra-fine alloy powder electromagnetic wave absorbent and preparation method thereof | |
| Lan et al. | In-situ synthesis of carbon nanotubes decorated by magnetite nanoclusters and their applications as highly efficient and enhanced microwave absorber | |
| CN106800916A (en) | A kind of graphene-based tri compound absorbing material and preparation method thereof | |
| Lv et al. | Facile synthesis of porous coin-like iron and its excellent electromagnetic absorption performance | |
| CN103667887A (en) | Preparation method of FeCo alloy absorbing material | |
| CN108941611A (en) | A kind of preparation method and product of ferromagnetic nano wire | |
| CN103586460A (en) | Magnetic porous cobalt hollow ball electromagnetic wave absorption material, preparation method and application thereof | |
| CN103333465A (en) | Preparation method of FeCo@MWNTs/epoxy resin based wave absorbing composite material | |
| CN112777582B (en) | Preparation method of nitrogen-doped ordered mesoporous carbon/cobalt metal composite material | |
| Liu et al. | Hierarchical magnetic core-shell nanostructures for microwave absorption: Synthesis, microstructure and property studies | |
| CN106398646A (en) | Coated-type electromagnetic inorganic nano composite wave absorbing material and preparation method and application thereof | |
| CN109699165B (en) | Three-dimensional porous manganese oxide-cobalt composite electromagnetic wave absorption material and preparation method and application thereof | |
| CN108822797B (en) | Titanium silicon carbon composite wave absorbing agent and preparation method and application thereof | |
| CN117550645A (en) | Preparation process and application of manganese zinc ferrite superfine powder | |
| CN110028930B (en) | HalS-Fe3O4@ C composite material and preparation method and application thereof | |
| CN109179381B (en) | Graphene/ferroferric oxide/copper silicate composite powder and preparation and application thereof | |
| CN103755333B (en) | Nano ferrite wave-absorbing material | |
| Ma et al. | Study on enhanced microwave absorption characteristics of annealed Fe3O4 |
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 |