CN114613564B - High-permeability ferrite magnetic material and preparation method thereof - Google Patents
High-permeability ferrite magnetic material and preparation method thereof Download PDFInfo
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- CN114613564B CN114613564B CN202210287547.9A CN202210287547A CN114613564B CN 114613564 B CN114613564 B CN 114613564B CN 202210287547 A CN202210287547 A CN 202210287547A CN 114613564 B CN114613564 B CN 114613564B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
- H01F1/0311—Compounds
- H01F1/0313—Oxidic compounds
- H01F1/0315—Ferrites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
- H01F1/342—Oxides
- H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
Abstract
The invention discloses a high-permeability ferrite magnetic material and a preparation method thereof, wherein the magnetic material comprises the following raw materials of 15-25 parts by weight of modified ferrite, 3-5 parts by weight of modified carrier, 6-8 parts by weight of isocyanate modified graphene oxide and 4-7 parts by weight of isocyanate modified carbon nano tube; the invention discloses a ferrite magnetic material with high magnetic conductivity and a preparation method thereof, the process design is reasonable, the component proportion is proper, the prepared ferrite magnetic material not only has excellent magnetic conductivity, but also can absorb electromagnetic waves in multiple dimensions so as to achieve the effect of high-efficiency absorption, and the ferrite magnetic material can be widely applied to various electromagnetic wave radiation environments and has high practicability.
Description
Technical Field
The invention relates to the technical field of ferrite, in particular to a high-permeability ferrite magnetic material and a preparation method thereof.
Background
Along with the progress and development of science and technology, electronic science and technology products gradually enter our lives, great convenience is brought to our lives, meanwhile, electromagnetic wave pollution is inevitable to appear in our lives, and researches show that the electromagnetic waves are contacted for a long time, great damage is caused to human bodies, various diseases such as nerve diseases, heredity diseases and the like are easily caused, and therefore, the wave absorbing material gradually becomes a research and development hotspot of our people.
The wave-absorbing material is a material capable of absorbing or greatly reducing the electromagnetic wave energy received by the surface of the wave-absorbing material so as to reduce the interference of the electromagnetic wave, and the research and development of the ferrite also bring new research results in the electromagnetic shielding direction, but the electromagnetic wave absorption effect of the wave-absorbing material prepared by the ferrite still cannot meet the requirements of people at present.
Aiming at the situation, a high-permeability ferrite magnetic material and a preparation method thereof are designed to solve the problem.
Disclosure of Invention
The invention aims to provide a ferrite magnetic material with high magnetic permeability and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the magnetic material comprises, by weight, 15-25 parts of modified ferrite, 3-5 parts of a modified carrier, 6-8 parts of isocyanate modified graphene oxide and 4-7 parts of isocyanate modified carbon nanotubes.
According to an optimized scheme, the modified ferrite is a rare earth doped cobalt ferrite, and is mainly prepared by reacting cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and citric acid.
According to an optimized scheme, the modified carrier is mainly prepared by the reaction of SBA-15, tetrabutyl titanate and 3-aminopropyltriethoxysilane.
In a more optimized scheme, the rare earth salt comprises any one of lanthanum nitrate hexahydrate and cerium nitrate hexahydrate or a mixture thereof.
According to an optimized scheme, the preparation method of the ferrite magnetic material with high magnetic permeability comprises the following steps:
1) Preparing raw materials;
2) Carrying out ultrasonic dispersion on SBA-15 and absolute ethyl alcohol, adding tetrabutyl titanate, stirring for reaction, transferring to a microwave condition after the reaction, reacting at 180-185 ℃, collecting precipitates after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying to obtain a pretreatment carrier;
3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring for dissolving, adding citric acid, continuously stirring, adjusting the pH value with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
4) Burning the pretreated carrier at 130-135 ℃ for 5-6h, transferring the calcined carrier into a 3-aminopropyltriethoxysilane solution, mixing and stirring, alternately washing chloroform and dichloromethane, and drying to obtain a modified carrier;
5) Taking the modified ferrite and dimethylformamide, stirring for dissolving, adding the modified carrier, stirring for reacting at 25-28 ℃, washing and drying to obtain a compound A;
6) Taking isocyanate modified graphene oxide, isocyanate modified carbon nano tubes and deionized water, carrying out ultrasonic dispersion, adding the compound A, carrying out ultrasonic oscillation, transferring to a high-pressure kettle, treating at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
The optimized scheme comprises the following steps:
1) Preparing raw materials;
2) Taking SBA-15 and absolute ethyl alcohol, performing ultrasonic dispersion for 1-2h, adding tetrabutyl titanate, stirring to react for 1-1.2h, transferring to a microwave condition after reaction, reacting for 30-35min at 180-185 ℃, collecting precipitate after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying at 70-80 ℃ to obtain a pretreatment carrier;
3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuously stirring for 3-4h, adjusting the pH value to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
4) Pretreating a carrier, burning for 5-6h at 130-135 ℃, transferring to a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing chloroform and dichloromethane, and drying to obtain a modified carrier;
5) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
6) Taking isocyanate modified graphene oxide, isocyanate modified carbon nano tubes and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring to an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
In an optimized scheme, in the step 3), the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, and the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
according to an optimized scheme, in the step 6), the preparation method of the isocyanate modified graphene oxide comprises the following steps: taking graphene oxide and dimethylformamide, performing ultrasonic dispersion for 20-30min, adding toluene diisocyanate and a tin catalyst, continuously stirring for 2-3h, stirring at 80-85 ℃ for reaction for 10-11h, centrifuging after reaction, washing and drying to obtain the isocyanate modified graphene oxide.
In an optimized scheme, in the step 6), the preparation method of the isocyanate modified carbon nanotube comprises the following steps: taking acidified carbon nano tubes and anhydrous toluene, carrying out ultrasonic dispersion for 0.5-1h in a nitrogen environment, adding toluene diisocyanate and a tin catalyst under oil bath at the temperature of 60-65 ℃, stirring for reaction for 8-10h, carrying out suction filtration washing, and carrying out vacuum drying to obtain the isocyanate modified carbon nano tubes.
In an optimized scheme, in the step 2), the microwave power is 200W-300W.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a high-permeability ferrite magnetic material and a preparation method thereof, wherein the material comprises a modified ferrite, a modified carrier, isocyanate modified graphene oxide and an isocyanate modified carbon nano tube, in the preparation process, firstly, the carrier SBA-15 and tetrabutyl titanate are selected, and titanium dioxide nanocrystals are loaded in a pore channel by utilizing a pore channel structure with the long-range order of the SBA-15 to obtain a pretreatment carrier; performing silanization modification on the surface of the modified carrier to obtain a modified carrier; because SBA-15 is a mesoporous molecular sieve, which has a two-dimensional hexagonal through hole structure, when the SBA-15 is used as a carrier, when electromagnetic waves enter a carrier pore channel, the hexagonal through hole structure can not only increase the reflection efficiency of the electromagnetic waves, but also effectively prevent the electromagnetic waves from returning to a radiation source after secondary reflection due to the existence of a straight pore channel structure, so that the transmission path of the electromagnetic waves in the carrier is improved, and high absorption is realized.
The modified ferrite is rare earth doped cobalt ferrite which is a permanent magnetic material with a spinel structure and has the properties of large magnetocrystalline anisotropy, high coercive force, high-frequency magnetic conductivity, excellent chemical stability and the like, and the doping of rare earth ions can refine the grain size and improve the magnetic performance; meanwhile, the introduction of rare earth ions can enable the surface silanized modified carrier to be assembled with the effective load, the loaded modified ferrite enters the pore channel of the SBA-15, the pore channel structure of the SBA-15 can inhibit the growth of the modified ferrite and the growth of titanium dioxide nanoparticles, and the modified ferrite and the titanium dioxide nanoparticles are in close contact in the process, so that a rich heterogeneous interface is formed, strong interface polarization is generated, electromagnetic waves are lost, and the electromagnetic wave absorption effect is further improved.
Isocyanate modified graphene oxide and isocyanate modified carbon nanotubes are introduced in the application, the carbon nanotubes are respectively subjected to surface modification during preparation, a large amount of isocyanate groups exist on the surfaces of the modified graphene oxide and the modified graphene oxide, a large amount of amino groups exist on the surface of the modified SBA-15, and the amino groups can be bonded with the isocyanate groups, so that the mutual interweaving and connecting conditions exist between the carbon nanotubes, between the carbon nanotubes and the graphene oxide, between the carbon nanotubes and the modified carrier, and between the graphene oxide and the modified carrier, thereby forming a mutual cross-linking three-dimensional structure, and the formation of the structure enables electromagnetic waves to undergo multiple reflection when passing through the multi-interface three-dimensional structure and the porous structure, so as to further improve the absorption capacity of the electromagnetic waves.
According to the preparation method, the rare earth doped cobalt ferrite with higher magnetic conductivity is selected, the magnetic loss capability of the rare earth doped cobalt ferrite is greatly improved, the prepared composite material has excellent dielectric loss and magnetic loss capability, and the wave-absorbing performance of the composite magnetic material is excellent.
The invention discloses a ferrite magnetic material with high magnetic conductivity and a preparation method thereof, the process design is reasonable, the component proportion is proper, the prepared ferrite magnetic material not only has excellent magnetic conductivity, but also can absorb electromagnetic waves in multiple dimensions so as to achieve the effect of high-efficiency absorption, and the ferrite magnetic material can be widely applied to various electromagnetic wave radiation environments and has high practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a ferrite magnetic material with high magnetic permeability comprises the following steps:
(1) Preparing raw materials;
(2) Taking SBA-15 and absolute ethyl alcohol, performing ultrasonic dispersion for 1-2h, adding tetrabutyl titanate, stirring to react for 1-1.2h, transferring to a microwave condition after reaction, reacting for 30-35min at 180-185 ℃, collecting precipitate after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying at 70-80 ℃ to obtain a pretreatment carrier; wherein the microwave power is 200W-300W;
(3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuing stirring for 3-4h, adjusting the pH to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
(4) Taking the pretreated carrier, burning for 5-6h at 130-135 ℃, transferring to a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing with chloroform and dichloromethane, and drying to obtain a modified carrier;
(5) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
(6) Taking graphene oxide and dimethylformamide, performing ultrasonic dispersion for 20-30min, adding toluene diisocyanate and a tin catalyst, continuously stirring for 2-3h, stirring at 80-85 ℃ for reaction for 10-11h, centrifuging after reaction, washing and drying to obtain the isocyanate modified graphene oxide.
Taking acidified carbon nano tubes and anhydrous toluene, carrying out ultrasonic dispersion for 0.5-1h in a nitrogen environment, adding toluene diisocyanate and a tin catalyst under oil bath at the temperature of 60-65 ℃, stirring for reaction for 8-10h, carrying out suction filtration washing, and carrying out vacuum drying to obtain the isocyanate modified carbon nano tubes.
Taking isocyanate modified graphene oxide, isocyanate modified carbon nano tubes and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring the compound A into an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
In the embodiment, the raw materials of each component of the magnetic material comprise, by weight, 15-25 parts of modified ferrite, 3-5 parts of modified carrier, 6-8 parts of isocyanate modified graphene oxide and 4-7 parts of isocyanate modified carbon nano tube;
the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, wherein the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
the frequency bandwidth of the sample prepared in the example 1, in which the reflectivity loss value is lower than-10 dB in 2-18GHz, is 4.7-17.2 GHz, and the minimum reflectivity loss value can reach-59.8 dB.
Example 2:
a preparation method of a ferrite magnetic material with high magnetic permeability comprises the following steps:
(1) Preparing raw materials;
(2) Taking SBA-15 and absolute ethyl alcohol, performing ultrasonic dispersion for 1-2h, adding tetrabutyl titanate, stirring to react for 1-1.2h, transferring to a microwave condition after reaction, reacting for 30-35min at 180-185 ℃, collecting precipitate after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying at 70-80 ℃ to obtain a pretreatment carrier; wherein the microwave power is 200W-300W;
(3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuously stirring for 3-4h, adjusting the pH value to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
(4) Taking the pretreated carrier, burning for 5-6h at 130-135 ℃, transferring to a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing with chloroform and dichloromethane, and drying to obtain a modified carrier;
(5) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
(6) Taking graphene oxide and dimethylformamide, performing ultrasonic dispersion for 20-30min, adding toluene diisocyanate and a tin catalyst, continuously stirring for 2-3h, stirring at 80-85 ℃ for reaction for 10-11h, centrifuging after reaction, washing and drying to obtain the isocyanate modified graphene oxide.
Taking acidified carbon nano tubes and anhydrous toluene, carrying out ultrasonic dispersion for 0.5-1h in a nitrogen environment, adding toluene diisocyanate and a tin catalyst under oil bath at the temperature of 60-65 ℃, stirring for reaction for 8-10h, carrying out suction filtration washing, and carrying out vacuum drying to obtain the isocyanate modified carbon nano tubes.
Taking isocyanate modified graphene oxide, isocyanate modified carbon nano tubes and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring to an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
In the embodiment, the raw materials of each component of the magnetic material comprise, by weight, 15-25 parts of modified ferrite, 3-5 parts of modified carrier, 6-8 parts of isocyanate modified graphene oxide and 4-7 parts of isocyanate modified carbon nano tube;
the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, wherein the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
the sample prepared in example 2 has a bandwidth with a reflectivity loss value of less than-10 dB in the range of 2-18GHz, which is 4.2-17.4 GHz, and the minimum reflectivity loss value can reach-60.2 dB.
Example 3:
a preparation method of a ferrite magnetic material with high magnetic permeability comprises the following steps:
(1) Preparing raw materials;
(2) Taking SBA-15 and absolute ethyl alcohol, performing ultrasonic dispersion for 1-2h, adding tetrabutyl titanate, stirring to react for 1-1.2h, transferring to a microwave condition after reaction, reacting for 30-35min at 180-185 ℃, collecting precipitate after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying at 70-80 ℃ to obtain a pretreatment carrier; wherein the microwave power is 200W-300W;
(3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuously stirring for 3-4h, adjusting the pH value to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
(4) Burning the pretreated carrier at 130-135 ℃ for 5-6h, transferring the calcined carrier into a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing chloroform and dichloromethane, and drying to obtain a modified carrier;
(5) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
(6) Taking graphene oxide and dimethylformamide, performing ultrasonic dispersion for 20-30min, adding toluene diisocyanate and a tin catalyst, continuously stirring for 2-3h, stirring at 80-85 ℃ for reaction for 10-11h, centrifuging after reaction, washing and drying to obtain the isocyanate modified graphene oxide.
Taking acidified carbon nano tubes and anhydrous toluene, carrying out ultrasonic dispersion for 0.5-1h in a nitrogen environment, adding toluene diisocyanate and a tin catalyst under oil bath at the temperature of 60-65 ℃, stirring for reaction for 8-10h, carrying out suction filtration washing, and carrying out vacuum drying to obtain the isocyanate modified carbon nano tubes.
Taking isocyanate modified graphene oxide, isocyanate modified carbon nano tubes and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring to an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
In the embodiment, the raw materials of each component of the magnetic material comprise, by weight, 15-25 parts of modified ferrite, 3-5 parts of modified carrier, 6-8 parts of isocyanate modified graphene oxide and 4-7 parts of isocyanate modified carbon nanotube;
the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, wherein the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
the sample prepared in example 3 has a bandwidth with a reflectivity loss value of less than-10 dB in the range of 2-18GHz as high as 4.5-17.2 GHz, and the minimum reflectivity loss value can reach-59.4 dB.
Comparative example 1:
a preparation method of a ferrite magnetic material with high magnetic permeability comprises the following steps:
(1) Preparing raw materials;
(2) Taking SBA-15 and absolute ethyl alcohol, performing ultrasonic dispersion for 1-2h, adding tetrabutyl titanate, stirring to react for 1-1.2h, transferring to a microwave condition after reaction, reacting for 30-35min at 180-185 ℃, collecting precipitate after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying at 70-80 ℃ to obtain a pretreatment carrier; wherein the microwave power is 200W-300W;
(3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuing stirring for 3-4h, adjusting the pH to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
(4) Burning the pretreated carrier at 130-135 ℃ for 5-6h, transferring the calcined carrier into a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing chloroform and dichloromethane, and drying to obtain a modified carrier;
(5) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
(6) Taking graphene oxide and dimethylformamide, performing ultrasonic dispersion for 20-30min, adding toluene diisocyanate and a tin catalyst, continuously stirring for 2-3h, stirring at 80-85 ℃ for reaction for 10-11h, centrifuging after reaction, washing and drying to obtain the isocyanate modified graphene oxide.
Taking isocyanate modified graphene oxide, a common carbon nano tube and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring to an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
In the embodiment, the magnetic material comprises the following raw materials, by weight, 15-25 parts of modified ferrite, 3-5 parts of modified carrier, 6-8 parts of isocyanate modified graphene oxide and 4-7 parts of common carbon nano tube;
the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, wherein the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
comparative example 1 is improved on the basis of example 2, common carbon nanotubes are added in the comparative example 1, and the rest of the process parameters and the component content are consistent with those of the example 2.
The frequency bandwidth of the sample prepared in the comparative example 1, in which the reflectivity loss value is lower than-10 dB in 2-18GHz, is 7.1-14.7 GHz, and the minimum reflectivity loss value can reach-51.2 dB.
Comparative example 2:
a preparation method of a ferrite magnetic material with high magnetic permeability comprises the following steps:
(1) Preparing raw materials;
(2) Taking SBA-15 and absolute ethyl alcohol, performing ultrasonic dispersion for 1-2h, adding tetrabutyl titanate, stirring to react for 1-1.2h, transferring to a microwave condition after reaction, reacting for 30-35min at 180-185 ℃, collecting precipitate after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying at 70-80 ℃ to obtain a pretreatment carrier; wherein the microwave power is 200W-300W;
(3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuously stirring for 3-4h, adjusting the pH value to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
(4) Burning the pretreated carrier at 130-135 ℃ for 5-6h, transferring the calcined carrier into a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing chloroform and dichloromethane, and drying to obtain a modified carrier;
(5) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
(6) Taking acidified carbon nano tubes and anhydrous toluene, carrying out ultrasonic dispersion for 0.5-1h in a nitrogen environment, adding toluene diisocyanate and a tin catalyst under oil bath at the temperature of 60-65 ℃, stirring for reaction for 8-10h, carrying out suction filtration washing, and carrying out vacuum drying to obtain the isocyanate modified carbon nano tubes.
Taking common graphene oxide, isocyanate modified carbon nano tubes and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring to an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
In the embodiment, the raw materials of each component of the magnetic material comprise, by weight, 15-25 parts of modified ferrite, 3-5 parts of modified carrier, 6-8 parts of common graphene oxide and 4-7 parts of isocyanate modified carbon nanotube;
the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, wherein the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
comparative example 2 is improved on the basis of example 2, common graphene oxide is added in the comparative example 2, and the rest of process parameters and component content are consistent with those of the example 2.
The sample prepared in the comparative example 2 has a bandwidth of 7.3-15.1 GHz with a reflectivity loss value of less than-10 dB in 2-18GHz, and the minimum reflectivity loss value can reach-52.4 dB.
Comparative example 3:
a preparation method of a ferrite magnetic material with high magnetic permeability comprises the following steps:
(1) Preparing raw materials;
(2) Taking SBA-15 and absolute ethyl alcohol, performing ultrasonic dispersion for 1-2h, adding tetrabutyl titanate, stirring to react for 1-1.2h, transferring to a microwave condition after reaction, reacting for 30-35min at 180-185 ℃, collecting precipitate after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying at 70-80 ℃ to obtain a pretreatment carrier; wherein the microwave power is 200W-300W;
(3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuously stirring for 3-4h, adjusting the pH value to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
(4) Burning the pretreated carrier at 130-135 ℃ for 5-6h, transferring the calcined carrier into a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing chloroform and dichloromethane, and drying to obtain a modified carrier;
(5) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
(6) Taking common graphene oxide, common carbon nano tubes and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring to an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
In the embodiment, the raw materials of each component of the magnetic material comprise, by weight, 15-25 parts of modified ferrite, 3-5 parts of modified carrier, 6-8 parts of common graphene oxide and 4-7 parts of common carbon nanotube;
the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, wherein the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
comparative example 3 is improved on the basis of example 2, common graphene oxide and common carbon nanotubes are added in the comparative example 3, and the rest of process parameters and component content are consistent with those of example 2.
The sample prepared in the comparative example 3 has a bandwidth of 8.9-12.4 GHz with a reflectivity loss value of less than-10 dB in 2-18GHz, and the minimum reflectivity loss value can reach-45.2 dB.
Comparative example 4:
a preparation method of a ferrite magnetic material with high magnetic permeability comprises the following steps:
(1) Preparing raw materials;
(2) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuing stirring for 3-4h, adjusting the pH to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
(3) Burning SBA-15 at 130-135 ℃ for 5-6h, transferring the burned SBA-15 into a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing chloroform and dichloromethane, and drying to obtain a modified carrier;
(4) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
(5) Taking graphene oxide and dimethylformamide, performing ultrasonic dispersion for 20-30min, adding toluene diisocyanate and a tin catalyst, continuously stirring for 2-3h, stirring at 80-85 ℃ for reaction for 10-11h, centrifuging after reaction, washing and drying to obtain the isocyanate modified graphene oxide.
Taking acidified carbon nano tubes and anhydrous toluene, carrying out ultrasonic dispersion for 0.5-1h in a nitrogen environment, adding toluene diisocyanate and a tin catalyst under oil bath at the temperature of 60-65 ℃, stirring and reacting for 8-10h, carrying out suction filtration and washing, and carrying out vacuum drying to obtain the isocyanate modified carbon nano tubes.
Taking isocyanate modified graphene oxide, isocyanate modified carbon nano tubes and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring the compound A into an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
In the embodiment, the raw materials of each component of the magnetic material comprise, by weight, 15-25 parts of modified ferrite, 3-5 parts of modified carrier, 6-8 parts of isocyanate modified graphene oxide and 4-7 parts of isocyanate modified carbon nanotube;
the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, wherein the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
comparative example 4 was modified from example 2, in comparative example 4 no titanium dioxide was introduced, and the remaining process parameters and component contents were identical to those of example 2.
The sample prepared in example 2 has a bandwidth with a reflectivity loss value of less than-10 dB in the range of 2-18GHz, which is 6.9-13.8 GHz, and the minimum reflectivity loss value can reach-54.6 dB.
And (4) conclusion: the invention discloses a ferrite magnetic material with high magnetic conductivity and a preparation method thereof, the process design is reasonable, the component proportion is proper, the prepared ferrite magnetic material not only has excellent magnetic conductivity, but also can absorb electromagnetic waves in multiple dimensions so as to achieve the effect of high-efficiency absorption, and the ferrite magnetic material can be widely applied to various electromagnetic wave radiation environments and has high practicability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a ferrite magnetic material with high magnetic permeability is characterized by comprising the following steps: the method comprises the following steps:
1) Preparing raw materials;
2) Taking SBA-15 and absolute ethyl alcohol, performing ultrasonic dispersion for 1-2h, adding tetrabutyl titanate, stirring to react for 1-1.2h, transferring to a microwave condition after reaction, reacting for 30-35min at 180-185 ℃, collecting precipitate after the reaction is finished, alternately washing with deionized water and absolute ethyl alcohol, and drying at 70-80 ℃ to obtain a pretreatment carrier;
3) Taking cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rare earth salt and deionized water, stirring and dissolving for 20-30min, adding citric acid, continuously stirring for 3-4h, adjusting the pH value to 3-4 with ammonia water, then placing in a drying box, carrying out heat preservation treatment for 4-4.5h at 80-85 ℃, heating to 100-105 ℃, carrying out heat preservation treatment for 20-22h, transferring to a muffle furnace, calcining for 4-5h at 700-720 ℃, and cooling to room temperature to obtain modified ferrite;
4) Taking the pretreated carrier, burning for 5-6h at 130-135 ℃, transferring to a 3-aminopropyltriethoxysilane solution, mixing and stirring for 14-16h, alternately washing with chloroform and dichloromethane, and drying to obtain a modified carrier;
5) Taking the modified ferrite and dimethylformamide, stirring and dissolving for 30-40min, adding the modified carrier, stirring and reacting for 40-45h at 25-28 ℃, washing and drying to obtain a compound A;
6) Taking isocyanate modified graphene oxide, isocyanate modified carbon nano tubes and deionized water, carrying out ultrasonic dispersion for 1-1.5h, adding the compound A, carrying out ultrasonic oscillation for 20-25min, transferring to an autoclave, carrying out treatment at 180-200 ℃ for 18-20h, taking out, washing, centrifuging and drying to obtain a finished product.
2. The method of claim 1, wherein the method comprises the steps of: in the step 3), the rare earth salt comprises lanthanum nitrate hexahydrate and cerium nitrate hexahydrate, wherein the mass ratio of the lanthanum nitrate hexahydrate to the cerium nitrate hexahydrate is 1:1.
3. the method of claim 1, wherein the method comprises the steps of: in the step 6), the preparation method of the isocyanate modified graphene oxide comprises the following steps: taking graphene oxide and dimethylformamide, performing ultrasonic dispersion for 20-30min, adding toluene diisocyanate and a tin catalyst, continuously stirring for 2-3h, stirring at 80-85 ℃ for reaction for 10-11h, centrifuging after reaction, washing and drying to obtain the isocyanate modified graphene oxide.
4. The method of claim 1, wherein the method comprises the steps of: in the step 6), the preparation method of the isocyanate modified carbon nano tube comprises the following steps: taking acidified carbon nano tubes and anhydrous toluene, carrying out ultrasonic dispersion for 0.5-1h in a nitrogen environment, adding toluene diisocyanate and a tin catalyst under oil bath at the temperature of 60-65 ℃, stirring for reaction for 8-10h, carrying out suction filtration washing, and carrying out vacuum drying to obtain the isocyanate modified carbon nano tubes.
5. The method for preparing the ferrite magnetic material with high magnetic permeability according to claim 1, characterized in that: in the step 2), the microwave power is 200W-300W.
6. The method of claim 1, wherein the method comprises the steps of: the magnetic material comprises, by weight, 15-25 parts of modified ferrite, 3-5 parts of a modified carrier, 6-8 parts of isocyanate modified graphene oxide and 4-7 parts of isocyanate modified carbon nano tubes.
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| WO2012089081A1 (en) * | 2010-12-28 | 2012-07-05 | 上海杰事杰新材料(集团)股份有限公司 | Nano particle/polyamide composite material, preparation method therefor, and use thereof |
| CN109321121A (en) * | 2018-09-26 | 2019-02-12 | 中国电子科技集团公司第三十三研究所 | A kind of nano combined suction wave slurry of carbon and preparation method thereof |
| WO2019109726A1 (en) * | 2017-12-08 | 2019-06-13 | 中车青岛四方机车车辆股份有限公司 | Electromagnetic shielding filler, electromagnetic shielding coating comprising same, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012089081A1 (en) * | 2010-12-28 | 2012-07-05 | 上海杰事杰新材料(集团)股份有限公司 | Nano particle/polyamide composite material, preparation method therefor, and use thereof |
| WO2019109726A1 (en) * | 2017-12-08 | 2019-06-13 | 中车青岛四方机车车辆股份有限公司 | Electromagnetic shielding filler, electromagnetic shielding coating comprising same, preparation method and application thereof |
| CN109321121A (en) * | 2018-09-26 | 2019-02-12 | 中国电子科技集团公司第三十三研究所 | A kind of nano combined suction wave slurry of carbon and preparation method thereof |
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