CN117894542A - Broadband high-conductivity manganese zinc ferrite material and preparation method thereof - Google Patents
Broadband high-conductivity manganese zinc ferrite material and preparation method thereof Download PDFInfo
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- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 52
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 43
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- 238000000034 method Methods 0.000 claims abstract description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- 229930192474 thiophene Natural products 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 16
- -1 thiophene Schiff base Chemical class 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011812 mixed powder Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000012744 reinforcing agent Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- DKGYESBFCGKOJC-UHFFFAOYSA-N thiophen-3-amine Chemical compound NC=1C=CSC=1 DKGYESBFCGKOJC-UHFFFAOYSA-N 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
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- 239000002131 composite material Substances 0.000 abstract description 16
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
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Abstract
The invention relates to the technical field of manganese zinc ferrite, and discloses a broadband high-conductivity manganese zinc ferrite material and a preparation method thereof, wherein a physical mixing method is adopted to prepare a composite material containing both conductive elements and magnetic elements, the manganese zinc ferrite has larger resistivity, electromagnetic waves can easily enter the material to realize electromagnetic impedance matching, so that the magnetic loss performance of the manganese zinc ferrite is outstanding; the polythiophene Schiff base conductive polymer can coordinate with metal ions to form a metal complex, so that the dielectric loss of the composite material is increased, and the reflection of electromagnetic waves on an incident interface is reduced; the Schiff base structure transfers charges by the conjugation of single and double bonds, double bond electrons rotate to enable the Schiff base structure to have magnetism, and meanwhile, the pinning effect of rare earth lanthanum increases the loss caused by domain wall resonance, so that the magnetic property and the wave absorbing property of the composite material are effectively improved, and the prepared manganese zinc ferrite material has the excellent properties of wide frequency and high conductivity.
Description
Technical Field
The invention relates to the technical field of manganese zinc ferrite, in particular to a broadband high-conductivity manganese zinc ferrite material and a preparation method thereof.
Background
With the wide application of electronic technology, the rapid development and popularization of radio broadcasting, mobile phones, televisions, microwave technology and other industries, electromagnetic radiation has become a novel pollutant, and electromagnetic waves have great harm to the environment and human bodies, so electromagnetic protection has become a hot spot for current research; according to the current development situation of the wave absorbing material, the traditional electromagnetic shielding material mainly achieves the purpose of shielding through the reflection of electromagnetic waves, and the comprehensive requirements of thinness, wideness, lightness and strength, which are proposed by increasingly higher stealth technologies, are difficult to meet, so that it is necessary to develop a protective material with high absorption and low reflection for electromagnetic waves.
The wave-absorbing material is used for electronic equipment, so that the radiation intensity of electromagnetic waves can be reduced, and the electromagnetic pollution is reduced to ensure the health of a human body; when being used as a wave absorbing material, the ferrite has high magnetic permeability and high coercivity, has small relative dielectric constant, is favorable for impedance matching, enhances the transmission and attenuation of electromagnetic waves, is expected to realize the absorption of microwaves in a high frequency band, but has the problems of large density, small temperature stability, low dielectric loss, narrow absorption band, weak absorption strength and the like, so that a single ferrite wave absorbing material cannot meet the requirements of strong absorption and wide frequency band at all, and therefore, two electromagnetic wave absorbing materials are often compounded, so that a new material has excellent characteristics, and the defect of the single wave absorbing material can be improved; the conductive polymer is a kind of wave-absorbing material with conjugated long chain structure, good dielectric property and strong dielectric loss capability, which can make up for the defect of ferrite dielectric loss, for example, patent CN102344648B discloses a wave-absorbing material compounded by conductive polymer/magnetic material, which consists of a-ferrite, poly (3, 4-dioxyethyl) thiophene and epoxy resin or polyurethane and other organic binders, the reflection loss value is preferably up to-17 dB, the wave-absorbing performance is improved to a certain extent, but the absorption bandwidth is still narrow, and the wave-absorbing material is not suitable for being applied to occasions with higher requirements on the absorption bandwidth.
The invention firstly synthesizes the polythiophene conductive polymer containing Schiff base, then prepares the lanthanum-doped Mn-Zn ferrite, combines the two by using a physical mixing method, retains the characteristic functional groups of the ferrite and the polymer, and has the characteristics of high absorption strength, wide absorption frequency band and excellent magnetic property.
Disclosure of Invention
The invention solves the technical problems that: the broadband high-conductivity Mn-Zn ferrite material and the preparation method thereof are provided, and the novel wave-absorbing material with good magnetic performance and wide absorption frequency band is obtained.
The technical scheme of the invention is as follows:
the preparation method of the broadband high-conductivity manganese-zinc ferrite material comprises the following components in parts by weight: 70-300 parts of polythiophene Schiff base conductive polymer and 100 parts of lanthanum-doped manganese zinc ferrite.
The preparation method comprises the following steps: placing the polythiophene Schiff base conductive polymer and the lanthanum-doped manganese-zinc ferrite into a beaker, adding tetrahydrofuran, carrying out ultrasonic treatment for 20-40min, mechanically stirring for 1-2h at the rotating speed of 1500-3000r/min, filtering, washing with deionized water, and drying to obtain the broadband high-conductivity manganese-zinc ferrite material.
Preferably, the preparation method of the lanthanum-doped manganese-zinc ferrite comprises the following steps: adding ferric oxide, manganese oxide, zinc oxide, lanthanum oxide and a grain boundary reinforcing agent into a ball mill for ball milling, then adding the ball mill into a muffle furnace, presintering for 1-4h at the temperature of 850-1000 , cooling to the room temperature along with the furnace, then performing secondary ball milling, then pressing and forming mixed powder, sintering at the sintering temperature of 1300-1450 for 3-5h, and naturally cooling to obtain the lanthanum-doped manganese zinc ferrite.
Preferably, the grain boundary strengthening agent is CaCO 3 SiO 2 Al 2 O 3 Any one of the following.
Preferably, the weight portions of the iron oxide are 55 to 65 portions, the manganese oxide is 20 to 35 portions, the zinc oxide is 5 to 15 portions, the lanthanum oxide is 0.02 to 0.2 portion and the grain boundary reinforcing agent is 0.1 to 0.5 portion.
Preferably, the preparation method of the polythiophene Schiff base conductive polymer comprises the following steps:
(1) Adding 2-imidazole formaldehyde and N, N-dimethylformamide into a reaction flask, stirring uniformly, adding thiophene-3-amine, stirring for reaction, adding deionized water after the reaction is finished, precipitating, filtering, recrystallizing methanol, and drying to obtain a thiophene Schiff base intermediate. The preparation process comprises the following steps:
(2) Adding ferric chloride and chloroform into a reaction flask, uniformly stirring, adding a thiophene Schiff base intermediate and thiophene, stirring for polymerization reaction, filtering after the reaction is finished, washing with deionized water, and drying to obtain the polythiophene Schiff base conductive polymer. The preparation process mechanism is as follows:
preferably, in the step (1), the weight part is 100 parts of 2-imidazole formaldehyde and 95-110 parts of thiophene-3-amine.
Preferably, the reaction temperature in the step (1) is 20-35 and the reaction time is 5-12h.
Preferably, in the step (2), 300-520 parts by weight of ferric chloride, 20-65 parts by weight of thiophene Schiff base intermediate and 100 parts by weight of thiophene are calculated.
Preferably, the polymerization temperature in the step (2) is 25-40 and the polymerization time is 8-16h. The beneficial technical effects of the invention are as follows:
according to the invention, a thiophene Schiff base intermediate is generated by reacting 2-imidazole formaldehyde with thiophene-3-amine, then the thiophene Schiff base intermediate and thiophene are subjected to polymerization reaction under the action of ferric trichloride to obtain a polythiophene Schiff base conductive polymer, then a lanthanum-doped manganese zinc ferrite is synthesized by a solid phase method by controlling the doping amount of lanthanum and adding a grain boundary reinforcing agent, and finally the polythiophene Schiff base conductive polymer and the lanthanum-doped manganese zinc ferrite are ultrasonically mixed by a physical mixing method to obtain the broadband high-conductivity manganese zinc ferrite material.
The composite material is prepared by adopting a physical mixing method, the tissue structure of any component of the polythiophene Schiff base conductive polymer and the lanthanum-doped manganese zinc ferrite is not damaged, and the characteristic functional groups of the ferrite and the polymer are reserved, so that the composite material contains both magnetic elements and conductive elements, and has conductivity and magnetic properties; the Mn-Zn ferrite has larger resistivity, electromagnetic waves can easily enter the material to realize electromagnetic impedance matching, so that the magnetic loss performance of the Mn-Zn ferrite is outstanding; the chemical bonding effect exists between the polythiophene Schiff base conductive polymer and the lanthanum-doped manganese zinc ferrite, so that the aggregation of ferrite nano particles is reduced to a certain extent, and certain defects can be formed in the ferrite after a proper amount of rare earth lanthanum element is added, so that the specific surface area of the material is improved, and the magnetic conductivity and the magnetic property of the material are further enhanced.
The polythiophene Schiff base conductive polymer containing hetero atoms can generate reflection loss due to polarization and dielectric loss, can coordinate with metal ions to form a metal complex, increases the dielectric loss and complex dielectric constant of the composite material, improves the impedance matching of the composite material, and reduces the reflection of electromagnetic waves on an incident interface; the Schiff base structure in the polymer has good conductivity and excellent coordination capacity, can form coordination with lanthanum ions in the Mn-Zn ferrite, the Schiff base transfers charges by the conjugation of single and double bonds, double bond electrons rotate to enable the Schiff base to have magnetism, the conjugation structure is matched with metal ions to generate additional polarization capacity and new electron transfer characteristics, and simultaneously, the single electron spin in the metal ions can generate a magnetic loss effect; in addition, the pinning effect of the rare earth lanthanum influences the movement of domain walls, so that the loss caused by resonance of the domain walls can be increased, and the microwave absorption capacity of the composite material is further effectively improved.
Compared with single-component Mn-Zn ferrite and polythiophene Schiff base conductive polymer, the broadband high-conductivity Mn-Zn ferrite material prepared by the invention has more excellent comprehensive wave absorbing capacity, and can effectively improve the absorption strength and the effective absorption frequency bandwidth by controlling the addition amount of the composite polythiophene Schiff base conductive polymer, thereby meeting the requirements of thinness, lightness, width and strength required by the novel wave absorbing material and further widening the application range of the Mn-Zn ferrite material.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
Examples
65 parts of ferric oxide, 25 parts of manganese oxide, 15 parts of zinc oxide, 0.02 part of lanthanum oxide and 0.1 part of grain boundary strengthening agent SiO 2 Adding the mixture into a ball mill for ball milling, then adding the mixture into a muffle furnace for presintering at 950 for 3 hours, cooling the mixture along with the furnace to room temperature, then performing secondary ball milling, then performing compression molding on the mixed powder, sintering the mixed powder at 1350 for 4 hours, and naturally cooling the mixed powder to obtain the lanthanum-doped manganese-zinc ferrite.
Examples
63 parts of ferric oxide, 20 parts of manganese oxide, 10 parts of zinc oxide, 0.11 part of lanthanum oxide and 0.3 part of grain boundary strengthening agent CaCO (CaCO) in parts by weight 3 Adding the mixture into a ball mill for ball milling, then adding the mixture into a muffle furnace, presintering the mixture for 1h at the temperature of 1000 , cooling the mixture to the room temperature along with the furnace, then performing secondary ball milling, then performing compression molding on the mixed powder, sintering the mixed powder at the sintering temperature of 1450 for 3h, and naturally cooling the mixed powder to obtain the lanthanum-doped manganese-zinc ferrite.
Examples
60 parts of ferric oxide, 30 parts of manganese oxide, 15 parts of zinc oxide, 0.2 part of lanthanum oxide and 0.5 part of grain boundary strengthening agent Al in parts by weight 2 O 3 Adding the mixture into a ball mill for ball milling, then adding the mixture into a muffle furnace for presintering at 900 for 3 hours, cooling the mixture along with the furnace to room temperature, then performing secondary ball milling, then performing compression molding on the mixed powder, sintering the mixed powder at 1300 for 5 hours, and naturally cooling the mixed powder to obtain the lanthanum-doped manganese-zinc ferrite.
Comparative example 1
65 parts of ferric oxide, 25 parts of manganese oxide, 15 parts of zinc oxide and 0.1 part of grain boundary reinforcing agent SiO 2 Adding the mixture into a ball mill for ball milling, then adding the mixture into a muffle furnace, presintering the mixture for 3 hours at the temperature of 950 , cooling the mixture to the room temperature along with the furnace, then performing secondary ball milling, then performing compression molding on the mixed powder, sintering the mixed powder at the sintering temperature of 1350 for 4 hours, and naturally cooling the mixed powder to obtain the manganese zinc ferrite.
Comparative example 2
Adding 65 parts of ferric oxide, 25 parts of manganese oxide, 15 parts of zinc oxide and 0.02 part of lanthanum oxide in parts by weight into a ball mill for ball milling, then adding into a muffle furnace for presintering at 950 for 3 hours, cooling to room temperature along with the furnace, then performing secondary ball milling, then pressing and forming mixed powder, sintering at 1350 for 4 hours, and naturally cooling to obtain the lanthanum-doped manganese zinc ferrite.
Saturation magnetic flux density test: the Mn-Zn ferrite was made into a ring size of X15X 8mm, and the saturation magnetic flux density was measured at 25and 50Hz at 1200A/m using a B-H/. Mu.Analyzer.
Initial permeability test: manganese zinc ferrite was made into rings of 20 158mm in size, wound 20 turns, and initial permeability was measured using an Agilent 4284A LCR precision tester at 25 , 10mV, 10 kHz.
As shown in the test data of the table, the magnetic permeability and the saturation magnetic flux density of the Mn-Zn ferrite are greatly improved along with the increase of the doping amount of lanthanum element and the content of grain boundary reinforcing agent of the Mn-Zn ferrite, and the initial magnetic permeability is up to 15031.4, because of the proper amount of La 2 O 3 The addition can form liquid phase sintering, improve the uniformity of the size of the sintered magnet crystal grains, promote the growth of the crystal grains, inhibit the growth of abnormal crystal grains, ensure that the uniformity of the grain size is good, improve the soft magnetic performance to a certain extent, further increase the initial permeability of ferrite and excessive La 2 O 3 The addition can separate out a mixed phase at the grain boundary, so that the magnetic performance of ferrite is reduced; simultaneous grain boundary strengthening agent CaCO 3 SiO 2 Or Al 2 O 3 The addition of the alloy mainly exists in the grain boundary, so that the chemical property of the grain boundary can be obviously improved, the growth of grains is prevented, a high-resistance layer is formed at the grain boundary, and the relative loss factor is reduced.
As the doping amount of lanthanum increases, the saturation magnetic flux density of ferrite is enhanced, the saturation magnetic flux density in the embodiment 2 reaches 550.3mT, the high saturation magnetic flux density of the material is realized, and meanwhile, the higher initial magnetic permeability and lower power consumption of the material are maintained; in comparative example 1, rare earth lanthanum was not doped, and the saturation magnetic flux density was only 432.4mT; comparative example 2, in which no grain boundary strengthener was added, had a saturation magnetic flux density of only 463.1mT and a low saturation magnetic flux density, resulted in poor magnetic properties.
Examples
(1) 50 parts of 2-imidazole formaldehyde and N, N-dimethylformamide in parts by weight are added into a reaction flask, uniformly stirred, 50 parts of thiophene-3-amine is added, deionized water is added after the reaction is carried out for 8 hours at 25 , precipitation is separated out, the solution is filtered, methanol is recrystallized, and a thiophene Schiff base intermediate is obtained after drying.
(2) 180 parts of ferric chloride and chloroform are added into a reaction flask according to parts by weight, uniformly stirred, 20 parts of thiophene Schiff base intermediate and 40 parts of thiophene are added, polymerization reaction is carried out at 35 , after reaction is carried out for 15 hours, filtration and deionized water washing are carried out, and the polythiophene Schiff base conductive polymer is obtained after drying.
(3) 70 parts of polythiophene Schiff base conductive polymer and 100 parts of lanthanum-doped manganese-zinc ferrite (prepared in example 1) in parts by weight are placed in a beaker, tetrahydrofuran is added, ultrasonic treatment is carried out for 25min, then mechanical stirring is carried out for 1.5h at the rotating speed of 2000r/min, after uniform mixing, filtration, deionized water washing and drying are carried out, and the broadband high-conductivity manganese-zinc ferrite material is obtained.
Examples
(1) 100 parts of 2-imidazole formaldehyde and N, N-dimethylformamide in parts by weight are added into a reaction flask, uniformly stirred, 95 parts of thiophene-3-amine are added, deionized water is added after reaction is carried out for 5 hours at 35 , precipitation is separated out, filtration and methanol recrystallization are carried out, and a thiophene Schiff base intermediate is obtained after drying.
(2) Adding 300 parts of ferric chloride and chloroform in parts by weight into a reaction flask, uniformly stirring, adding 20 parts of thiophene Schiff base intermediate and 100 parts of thiophene, performing polymerization reaction at 40 , reacting for 8 hours, filtering, washing with deionized water, and drying to obtain the polythiophene Schiff base conductive polymer.
(3) 180 parts of polythiophene Schiff base conductive polymer and 100 parts of lanthanum-doped manganese-zinc ferrite (prepared in example 2) in parts by weight are placed in a beaker, tetrahydrofuran is added, ultrasonic treatment is carried out for 40min, then mechanical stirring is carried out for 1h at the rotating speed of 3000r/min, after uniform mixing, filtration, deionized water washing and drying are carried out, and the broadband high-conductivity manganese-zinc ferrite material is obtained.
Examples
(1) Adding 80 parts of 2-imidazole formaldehyde and N, N-dimethylformamide in parts by weight into a reaction flask, uniformly stirring, adding 88 parts of thiophene-3-amine, reacting for 12 hours at 20 , adding deionized water, precipitating, filtering, recrystallizing methanol, and drying to obtain a thiophene Schiff base intermediate.
(2) Adding 520 parts of ferric chloride and chloroform in parts by weight into a reaction flask, uniformly stirring, adding 65 parts of thiophene Schiff base intermediate and 100 parts of thiophene, performing polymerization reaction at 25 , reacting for 16 hours, filtering, washing with deionized water, and drying to obtain the polythiophene Schiff base conductive polymer.
(3) 300 parts of polythiophene Schiff base conductive polymer and 100 parts of lanthanum-doped manganese-zinc ferrite (prepared in example 3) in parts by weight are placed in a beaker, tetrahydrofuran is added, ultrasonic treatment is carried out for 40min, then mechanical stirring is carried out for 2h at the rotating speed of 1500r/min, after uniform mixing, filtration, deionized water washing and drying are carried out, and the broadband high-conductivity manganese-zinc ferrite material is obtained.
Comparative example 3
(3) 70 parts of polythiophene Schiff base conductive polymer (prepared from example 4) and 100 parts of manganese zinc ferrite (prepared from comparative example 1) in parts by weight are placed in a beaker, tetrahydrofuran is added, ultrasonic treatment is carried out for 25min, then mechanical stirring is carried out for 1.5h at the rotating speed of 2000r/min, after uniform mixing, filtration, washing with deionized water and drying are carried out, thus obtaining the manganese zinc ferrite material.
Comparative example 4
(3) 70 parts of polythiophene Schiff base conductive polymer (prepared from example 4) and 100 parts of lanthanum-doped manganese zinc ferrite (prepared from comparative example 2) in parts by weight are placed in a beaker, tetrahydrofuran is added, ultrasonic treatment is carried out for 25min, then mechanical stirring is carried out for 1.5h at the rotating speed of 2000r/min, after uniform mixing, filtration and deionized water washing are carried out, and a manganese zinc ferrite material is obtained after drying.
Comparative example 5 is a polythiophene schiff base conductive polymer (prepared from example 4).
Wave absorbing performance test: the materials to be tested prepared in the examples and the comparative examples are prepared into annular samples with the outer diameter of 7mm, the inner diameter of 3mm and the height of 2mm according to the mass ratio of the materials to paraffin of 7:3, and the wave absorbing performance of the materials in the frequency range of 2-18GHz is tested by adopting a network analyzer.
As can be seen from the test data of the table, in the embodiment, as the content of the polythiophene Schiff base conductive polymer increases, the reflection loss value of the material increases from-28.5 dB to-39.5 dB, the bandwidth less than or equal to-10 dB reaches 4.8GHz at most, the absorption intensity is high, and the absorption frequency bandwidth is high, because on one hand, the polythiophene Schiff base conductive polymer containing hetero atoms has polarization and dielectric loss, thereby causing reflection loss, and can coordinate with metal ions to form conjugated polymer metal complex, thereby increasing the dielectric loss and complex dielectric constant of the composite material, improving the impedance matching of the composite material and reducing the reflection of electromagnetic waves on an incident interface; the conjugated Schiff base structure in the polymer has good conductivity and excellent coordination capacity, and forms coordination with lanthanum ions in the Mn-Zn ferrite, the Schiff base can transfer charges through the conjugation of single and double bonds, double bond electrons of the Schiff base rotate to enable the Schiff base to have magnetism, the conjugated structure is matched with metal ions to generate additional polarization capacity and new electron transfer characteristics, and simultaneously, single electron spin in the metal ions can generate a magnetic loss effect, so that the wave absorbing capacity is improved; on the other hand, the chemical bonding effect exists between the polythiophene Schiff base conductive polymer and the ferrite, the aggregation of ferrite nano particles is reduced to a certain extent, the composite particles have conductivity and magnetic property, the conductivity is enhanced along with the increase of the polythiophene content, and electromagnetic waves can be absorbed for many times by the lanthanum-doped manganese zinc ferrite and the polythiophene Schiff base conductive polymer, so that the electromagnetic waves entering the material are absorbed to the greatest extent, the electromagnetic waves are prevented from reentering the space, and the wave absorbing performance of the composite material is improved.
Comparative example 3 is a composite material of manganese-zinc ferrite and polythiophene schiff base conductive polymer without lanthanum, the reflection loss value is-21.8 dB, comparative example 4 is a composite material of manganese-zinc ferrite and polythiophene schiff base conductive polymer without grain boundary reinforcing agent, the reflection loss value is-23.5 dB, and it is indicated that the doping of rare earth lanthanum is beneficial to improving the wave absorbing performance of the material, because the pinning effect of rare earth lanthanum affects the domain wall movement, the loss caused by domain wall resonance can be increased, and the microwave absorbing capability of the composite material is further effectively improved; comparative example 5 is a single-component polythiophene schiff base conductive polymer, the reflection loss value is-6.2 dB, and the wave absorbing performance is poor; therefore, compared with the polythiophene Schiff base conductive polymer and the lanthanum-doped ferrite, the composite wave absorbing performance is more excellent, and the effective absorption frequency band and the absorption strength are further improved.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown, it is well suited to various fields of use for which the invention is suited, and further modifications may be readily made by one skilled in the art, and the invention is therefore not to be limited to the particular details and examples shown and described herein, without departing from the general concepts defined by the claims and the equivalents thereof.
Claims (9)
1. The preparation method of the broadband high-conductivity manganese-zinc ferrite material is characterized by comprising the following components in parts by weight: 70-300 parts of polythiophene Schiff base conductive polymer and 100 parts of lanthanum-doped manganese zinc ferrite;
the preparation method comprises the following steps: placing the polythiophene Schiff base conductive polymer and the lanthanum-doped manganese-zinc ferrite into a beaker, adding tetrahydrofuran, carrying out ultrasonic treatment for 20-40min, mechanically stirring for 1-2h at the rotating speed of 1500-3000r/min, filtering, washing with deionized water, and drying to obtain the broadband high-conductivity manganese-zinc ferrite material.
2. The preparation method of the broadband high-conductivity manganese-zinc ferrite material according to claim 1, which is characterized by comprising the following steps: adding ferric oxide, manganese oxide, zinc oxide, lanthanum oxide and a grain boundary reinforcing agent into a ball mill for ball milling, then adding the ball mill into a muffle furnace, presintering for 1-4h at the temperature of 850-1000 , cooling to the room temperature along with the furnace, then performing secondary ball milling, then pressing and forming mixed powder, sintering at the sintering temperature of 1300-1450 for 3-5h, and naturally cooling to obtain the lanthanum-doped manganese zinc ferrite.
3. The method for preparing a broadband high-conductivity manganese-zinc ferrite material according to claim 1, wherein the grain boundary reinforcing agent is CaCO 3 SiO 2 Al 2 O 3 Any one of the following.
4. The preparation method of the broadband high-conductivity manganese-zinc ferrite material according to claim 1, wherein the weight parts of the iron oxide are 55-65 parts, the weight parts of the manganese oxide are 20-35 parts, the weight parts of the zinc oxide are 5-15 parts, the weight parts of the lanthanum oxide are 0.02-0.2 part, and the weight parts of the grain boundary reinforcing agent are 0.1-0.5 part.
5. The preparation method of the broadband high-conductivity manganese-zinc ferrite material according to claim 1, wherein the preparation method of the polythiophene schiff base conductive polymer is carried out according to the following steps:
(1) Adding 2-imidazole formaldehyde and N, N-dimethylformamide into a reaction flask, uniformly stirring, adding thiophene-3-amine, stirring for reaction, adding deionized water after the reaction is finished, precipitating precipitate, filtering, recrystallizing methanol, and drying to obtain a thiophene Schiff base intermediate;
(2) Adding ferric chloride and chloroform into a reaction flask, uniformly stirring, adding a thiophene Schiff base intermediate and thiophene, stirring for polymerization reaction, filtering after the reaction is finished, washing with deionized water, and drying to obtain the polythiophene Schiff base conductive polymer.
6. The method for preparing a broadband high-conductivity manganese-zinc ferrite material according to claim 5, wherein in the step (1), 100 parts of 2-imidazole formaldehyde and 95-110 parts of thiophene-3-amine are calculated according to parts by weight.
7. The method for preparing a broadband high-conductivity manganese-zinc ferrite material according to claim 5, wherein the reaction temperature in the step (1) is 20-35 and the reaction time is 5-12h.
8. The method for preparing the broadband high-conductivity manganese-zinc ferrite material according to claim 5, wherein in the step (2), 300-520 parts of ferric chloride, 20-65 parts of thiophene Schiff base intermediate and 100 parts of thiophene are calculated according to parts by weight.
9. The method for preparing a broadband high-conductivity manganese-zinc ferrite material according to claim 5, wherein the polymerization temperature in the step (2) is 25-40 and the polymerization time is 8-16h.
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| US2551711A (en) * | 1943-07-01 | 1951-05-08 | Hartford Nat Bank & Trust Co | Manganese zinc ferrite core |
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| CN112625441A (en) * | 2020-12-17 | 2021-04-09 | 集美大学 | Manganese-zinc ferrite/polyaniline/titanium carbide composite wave-absorbing material and preparation method thereof |
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| US2551711A (en) * | 1943-07-01 | 1951-05-08 | Hartford Nat Bank & Trust Co | Manganese zinc ferrite core |
| CN1403406A (en) * | 2002-09-29 | 2003-03-19 | 武汉大学 | Electromagnetic wave absorbing material containing carbon covered metal or metal compound and its application |
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