CN117466338A - Fe@MoS 2 SiCN precursor ceramic composite wave-absorbing material and preparation method thereof - Google Patents
Fe@MoS 2 SiCN precursor ceramic composite wave-absorbing material and preparation method thereof Download PDFInfo
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- 239000011358 absorbing material Substances 0.000 title claims abstract description 42
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 239000002244 precipitate Substances 0.000 claims description 23
- 238000009210 therapy by ultrasound Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
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- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 8
- 239000005695 Ammonium acetate Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 229940043376 ammonium acetate Drugs 0.000 claims description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical group [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 8
- 239000012700 ceramic precursor Substances 0.000 abstract 1
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- 229910010293 ceramic material Inorganic materials 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
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- 230000005670 electromagnetic radiation Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- 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
Abstract
The invention discloses a Fe@MoS 2 The SiCN precursor ceramic composite wave-absorbing material and the preparation method thereof comprise the following preparation processes: first with FeCl 3 ·6H 2 O is the iron source to prepare hollow Fe 3 O 4 Nano particles, then molybdenum salt and thiourea are used as raw materials to undergo hydrothermal reaction, and hollow Fe is obtained 3 O 4 In situ generation of MoS on nanoparticles 2 Nano-sheet to form Fe@MoS 2 Finally, the compound takes polycarbosilane as ceramic precursor liquid to prepare Fe@MoS through the processes of ball milling, pressing into blanks, cold isostatic pressing and high-temperature sintering after the crosslinking curing reaction 2 SiCN precursor ceramic composite wave-absorbing material. Fe@MoS of the invention 2 The SiCN precursor ceramic composite wave-absorbing material has wider wave-absorbing bandwidth and stronger wave-absorbing capacity, and has simple production process and good application prospect in the wave-absorbing material.
Description
Technical Field
The invention relates to the field of ceramic matrix composite wave-absorbing materials, in particular to Fe@MoS 2 A SiCN precursor ceramic composite wave-absorbing material and a preparation method thereof.
Background
Along with the development of modern technology, electromagnetic waves are widely applied to the technical fields of wireless communication, data transmission, satellite transmission, radar stealth and the like. The advanced wireless communication transmission system needs electromagnetic wave absorption in a wide frequency range, meanwhile, electromagnetic wave interference between the systems causes the phenomenon that electronic equipment is out of order, electromagnetic radiation can cause direct and indirect harm to human bodies, electromagnetic pollution caused by electromagnetic waves seriously threatens the health work and life of human beings, and therefore effective shielding or absorbing of the electromagnetic waves is a problem which needs to be solved in the current information society. In addition, because of the urgent need of modern war for new weapons, development of stealth technology becomes a strategic point for improving national military forces and getting important status in international society, so research and development and application of electromagnetic wave absorbing materials are used as technical cores of radar stealth materials, and become the primary direction of material research in military fields. The application research of the wave-absorbing material has a crucial influence on the development of civil electromagnetic radiation industry and military stealth technology.
The electromagnetic shielding is to surround the interference source by shielding materials so as to prevent the interference electromagnetic field from diffusing outwards, and surround the receiving system by shielding materials so as to shield the influence of the external interference electromagnetic field on the receiving system. Electromagnetic interference can not be fundamentally solved through an electromagnetic screen, however, the electromagnetic wave absorbing material can consume electromagnetic wave energy incident in space through absorption, attenuation and conversion and reduce or eliminate reflected electromagnetic waves, so that the research of the electromagnetic wave absorbing material has very important significance.
Ideal electromagnetic wave absorbing material materials are required to have a thin thickness, low density, broad absorption bandwidth and strong absorption capacity. The core of the wave absorbing material is an absorbent material with good electromagnetic wave absorbing performance, so that the requirements of thin, wide, light, strong and the like of the wave absorbing material are met, and the research of the absorbent needs multi-directional co-development.
The precursor ceramic is a ceramic material obtained by directly pyrolyzing an organic polymer precursor. The precursor pyrolysis method is only a novel ceramic preparation process and has a plurality of advantages which are incomparable with the traditional ceramic process. The SiCN precursor ceramic has good thermal stability, creep resistance and dielectric property, low density, uniform and stable structure and is considered to have certain potential in the aspect of wave absorbing property. However, siCN precursor ceramics have poor wave-absorbing properties, which greatly limits their development in the field of wave-absorbing materials.
The electric property and dielectric property of the material can be improved by adjusting resistivity and electromagnetic parameters by introducing active fillers such as transition metal elements Fe, mo and the like into ceramic matrixes such as SiCN and the like, the resistivity is reduced, the dielectric constant and dielectric loss are increased, and the material has magnetism and generates magnetic loss due to the introduction of magnetic elements, so that the material can be used for improving the wave absorbing property.
Recently, transition metal MoS having a graphite-like layered structure 2 The material has high specific surface area and special electronic property, so that the material becomes a novel mechanical alloying material. MoS (MoS) 2 The large specific surface area of the composite material increases the receiving area of the electromagnetic wave, can further cause the electromagnetic wave to form multiple reflection loss between sheets, is beneficial to the electromagnetic wave to enter the absorber and further attenuate the incident wave, and is a promising electromagnetic wave absorbing material. By magnetic material Fe 3 O 4 Nanoparticle and dielectric loss material MoS 2 Not only complex Fe 3 O 4 Poor impedance matching and small absorption bandwidth, and because of MoS 2 Can reduce the quality of the material. Fe@MoS 2 The composite is introduced into SiCN precursor ceramic to raise the electron transmission capacity of the material and to further improve the impedance matching performance of the precursor ceramic material, so as to provide excellent wave absorbing performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a Fe@MoS 2 The SiCN precursor ceramic composite wave-absorbing material and the preparation method thereof comprise the following preparation processes:
step 1: preparation of hollow Fe by hydrothermal method 3 O 4 A nanoparticle; step 2: in-situ precipitation reaction for preparing Fe@MoS 2 A complex; step 3: precursor conversion method for preparing Fe@MoS 2 SiCN precursor ceramic composite wave-absorbing material.
Further, the hydrothermal method in the step 1 prepares hollow Fe 3 O 4 The specific process of the nano particle is as follows: feCl is added 3 ·6H 2 O is dissolved in glycol and is subjected to ultrasonic treatment to form a transparent yellow solution, then ammonium acetate is added into the transparent yellow solution and is subjected to continuous ultrasonic treatment for 1 hour, and then the transparent yellow solution is transferred into tetrafluoroethyleneIn a stainless steel autoclave lined with a liner, heating at 200deg.C for 8h to obtain black precipitate, centrifuging with ethanol, washing three times, and vacuum drying at 60deg.C to obtain hollow Fe 3 O 4 A nanoparticle; the step 2 prepares Fe@MoS 2 The specific process of the compound is as follows: weighing molybdenum salt and thiourea, dissolving in deionized water, magnetically stirring until the molybdenum salt and thiourea are completely dissolved, and then weighing hollow Fe 3 O 4 Stirring the nano particles in a solution, placing the solution in an ultrasonic cleaner after stirring by using a glass rod until the solution is black turbid liquid, transferring the liquid into a polytetrafluoroethylene lining of a reaction kettle, obtaining a precipitate after hydrothermal reaction, washing the precipitate with absolute ethyl alcohol for three times, and then drying and grinding the precipitate; the step 3 prepares Fe@MoS 2 The specific process of the SiCN precursor ceramic composite wave-absorbing material is as follows: adding polycarbosilane and diisopropyl peroxide into a reaction kettle, adding methacrylic acid for full dissolution, and adding prepared Fe@MoS into the reaction kettle 2 After the compound is fully dissolved and crosslinked and solidified, fe@MoS is prepared through ball milling, blank pressing, cold isostatic pressing and high-temperature sintering 2 SiCN precursor ceramic composite wave-absorbing material.
Further, the FeCl 3 ·6H 2 The weight ratio of O to ammonium acetate is 10:3-10:9; the weight ratio of the molybdenum salt to the thiourea is 1:1-1:6, and the hollow Fe is as follows 3 O 4 The weight ratio of the nano particles to the molybdenum salt is 1:2-1:4; the weight ratio of the polycarbosilane to the diisopropyl peroxide to the methacrylic acid is 100 (8-12) (3-5), and the polycarbosilane to the Fe@MoS 2 The weight ratio of the compound is 100:5-100:10.
Further, the molybdenum salt is sodium molybdate dihydrate (Na 2 MoO 4 ·2H 2 O), ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) one of the following.
Further, the hydrothermal reaction is carried out at a reaction temperature of 150-220 ℃ for 12-24 hours.
Further, the crosslinking and curing reaction is to heat up to 300-600 ℃ at a heating rate of 5 ℃/min, and keep the temperature for 2-4 h.
Further, the ball milling is to put the sample into a vibration ball mill for ball milling for 1-5 hours, then the powder is sieved by a 100-200 mesh sieve, and the cold isostatic pressing is carried out for 3min under the pressure of 180 Mpa.
Further, the high-temperature sintering is performed in an inert gas atmosphere, the sintering temperature is 1100-1400 ℃, the sintering time is 0.5-1.5 h, and the inert gas is one of nitrogen, argon, helium and neon.
Furthermore, the invention also provides the Fe@MoS prepared by the method 2 SiCN precursor ceramic composite wave-absorbing material.
It is noted that Fe@MoS prepared by the method 2 SiCN precursor ceramic composite wave-absorbing material takes SiCN precursor ceramic as a matrix and loads Fe with hollow structure 3 O 4 The nano particles lighten the density of materials and increase the multiple reflection loss of electromagnetic waves in the hollow structure; and at Fe 3 O 4 Successful growth of MoS on nanoparticles 2 The sheet structure not only effectively improves the specific surface area of the whole material and increases the receiving area of electromagnetic waves, but also enables the electromagnetic waves to form multiple reflection loss among sheets and effectively adjusts the impedance matching characteristic.
The invention provides an Fe@MoS 2 The SiCN precursor ceramic composite wave-absorbing material and the preparation method thereof can realize the following beneficial effects:
(1) The invention adopts a precursor conversion method, the preparation process is simple, and the obtained material has excellent high temperature resistance and wide application range.
(2) The SiCN precursor ceramic has excellent dielectric property, and Fe@MoS with flower-like structure and magnetic property is introduced into the SiCN precursor ceramic 2 The three materials form a three-dimensional conductive network structure and an interface polarization effect, and the composite material is endowed with good resistance type loss and magnetic loss performance through good magnetic performance, so that the impedance matching performance of the composite material is enhanced under the synergistic effect, and an excellent wave absorbing effect is shown.
Detailed Description
The technical solutions of the present invention will be clearly and completely described 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, 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.
In addition, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the technical solutions, and when the technical solutions are contradictory or cannot be implemented, the combination of the technical solutions should be considered as not existing, and not falling within the scope of protection claimed by the present invention.
Example 1
Step 1: preparation of Fe 3 O 4 Nanoparticles: 10mg of FeCl is taken 3 ·6H 2 O is dissolved in glycol and is subjected to ultrasonic treatment to form transparent yellow solution, then 3mg of ammonium acetate is added into the transparent yellow solution and is subjected to continuous ultrasonic treatment for 1h, then the transparent yellow solution is transferred into a stainless steel autoclave with a tetrafluoroethylene lining, and is heated for 8h at the temperature of 200 ℃ to obtain black precipitate, and then the black precipitate is subjected to centrifugal washing by ethanol for three times and is dried in vacuum at the temperature of 60 ℃ to obtain hollow Fe 3 O 4 And (3) nanoparticles.
Step 2: preparation of Fe@MoS 2 A complex: 10mg of Na was weighed 2 MoO 4 ·2H 2 Dissolving O molybdenum salt and 10mg of thiourea in deionized water, magnetically stirring until the O molybdenum salt and the thiourea are completely dissolved, and weighing 5mg of hollow Fe 3 O 4 The nano particles are placed in a solution, stirred by a glass rod, placed in an ultrasonic cleaner for ultrasonic treatment for 15min until the solution is black turbid liquid, then the liquid is transferred into a polytetrafluoroethylene lining of a reaction kettle, the temperature of the reaction kettle is raised to 150 ℃, the reaction kettle is kept for 24h for hydrothermal reaction to obtain a precipitate product, and the precipitate product is washed by absolute ethyl alcohol for three times and then dried and ground.
Step 3: preparation of Fe@MoS 2 SiCN precursor ceramic composite wave-absorbing material: 100mg of polycarbosilane was addedAnd 8mg of diisopropyl peroxide are added into a reaction kettle, then 3mg of methacrylic acid is added for full dissolution, and 10mg of prepared Fe@MoS is added into the reaction kettle 2 The composite is fully dissolved, the temperature is raised to 300 ℃ at the heating rate of 5 ℃/min, the cross-linking curing reaction is completed after the temperature is kept for 4 hours, a cured block body is obtained, the block body material is put into a vibration ball mill for ball milling for 1 hour, then a 100-mesh sieve is used for obtaining powder with the particle size of about 149 mu m, the powder is pressed into a green body and is pressed for 3 minutes under 180MPa in a cold isostatic pressing way, finally the pressed material is sintered at high temperature under nitrogen atmosphere, the sintering temperature is 1100 ℃ and the sintering time is 1.5 hours, and finally Fe@MoS is obtained 2 SiCN precursor ceramic composite wave-absorbing material.
Example 2
Step 1: preparation of Fe 3 O 4 Nanoparticles: 10mg of FeCl is taken 3 ·6H 2 O is dissolved in glycol and is subjected to ultrasonic treatment to form transparent yellow solution, then 6mg of ammonium acetate is added into the transparent yellow solution and is subjected to continuous ultrasonic treatment for 1h, then the transparent yellow solution is transferred into a stainless steel autoclave with a tetrafluoroethylene lining, and is heated for 8h at the temperature of 200 ℃ to obtain black precipitate, and then the black precipitate is subjected to centrifugal washing by ethanol for three times and is dried in vacuum at the temperature of 60 ℃ to obtain hollow Fe 3 O 4 And (3) nanoparticles.
Step 2: preparation of Fe@MoS 2 A complex: 10mg (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Dissolving O molybdenum salt and 30mg of thiourea in deionized water, magnetically stirring until the O molybdenum salt and the thiourea are completely dissolved, and weighing 2.5mg of hollow Fe 3 O 4 The nano particles are placed in a solution, stirred by a glass rod, placed in an ultrasonic cleaner for ultrasonic treatment for 15min until the solution is black turbid liquid, then the liquid is transferred into a polytetrafluoroethylene lining of a reaction kettle, the temperature of the reaction kettle is raised to 200 ℃, the reaction kettle is kept for 18h for hydrothermal reaction to obtain a precipitate product, and the precipitate product is washed by absolute ethyl alcohol for three times and then dried and ground.
Step 3: preparation of Fe@MoS 2 SiCN precursor ceramic composite wave-absorbing material: 100mg of polycarbosilane and 10mg of diisopropyl peroxide were added to a reaction vessel, followed by addition ofAfter 4mg methacrylic acid was sufficiently dissolved, 8mg of the prepared Fe@MoS was added to the reaction vessel 2 The composite is fully dissolved, then the temperature is increased to 500 ℃ at the heating rate of 5 ℃/min, the cross-linking curing reaction is completed for 3 hours, the cured block is obtained, the block material is put into a vibration ball mill for ball milling for 5 hours, then a 200-mesh sieve is used for obtaining powder with the grain diameter of about 74 mu m, the powder is pressed into a green body and is pressed for 3 minutes under 180MPa in a cold isostatic pressing way, finally the pressed material is sintered at high temperature under nitrogen atmosphere, the sintering temperature is 1300 ℃ and the sintering time is 1 hour, and finally Fe@MoS is obtained 2 SiCN precursor ceramic composite wave-absorbing material.
Example 3
Step 1: preparation of Fe 3 O 4 Nanoparticles: 10mg of FeCl is taken 3 ·6H 2 O is dissolved in glycol and is subjected to ultrasonic treatment to form transparent yellow solution, then 9mg of ammonium acetate is added into the transparent yellow solution and is subjected to continuous ultrasonic treatment for 1h, then the transparent yellow solution is transferred into a stainless steel autoclave with a tetrafluoroethylene lining, and is heated for 8h at the temperature of 200 ℃ to obtain black precipitate, and then the black precipitate is subjected to centrifugal washing by ethanol for three times and is dried in vacuum at the temperature of 60 ℃ to obtain hollow Fe 3 O 4 And (3) nanoparticles.
Step 2: preparation of Fe@MoS 2 A complex: 10mg (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Dissolving O molybdenum salt and 60mg of thiourea in deionized water, magnetically stirring until the O molybdenum salt and the thiourea are completely dissolved, and weighing 5mg of hollow Fe 3 O 4 The nano particles are placed in a solution, stirred by a glass rod, placed in an ultrasonic cleaner for ultrasonic treatment for 15min until the solution is black turbid liquid, then the liquid is transferred into a polytetrafluoroethylene lining of a reaction kettle, the temperature of the reaction kettle is raised to 220 ℃, the reaction kettle is kept for 12h for hydrothermal reaction to obtain a precipitate product, and the precipitate product is washed by absolute ethyl alcohol for three times and then dried and ground.
Step 3: preparation of Fe@MoS 2 SiCN precursor ceramic composite wave-absorbing material: 100mg of polycarbosilane and 12mg of diisopropyl peroxide are added into a reaction kettle, then 5mg of methacrylic acid is added for full dissolution, and 5mg of prepared Fe@is added into the reaction kettleMoS 2 The composite is fully dissolved, then the temperature is increased to 600 ℃ at the heating rate of 5 ℃/min, the heat preservation is carried out for 2 hours to complete the crosslinking curing reaction, the cured block is obtained, the block material is put into a vibration ball mill for ball milling for 3 hours, then a 100-mesh sieve is used for obtaining powder with the particle size of about 149 mu m, the powder is pressed into a green body and is pressed for 3 minutes under 180MPa by cold isostatic pressing, finally the pressed material is sintered at high temperature under argon atmosphere, the sintering temperature is 1400 ℃ and the sintering time is 0.5 hour, and finally Fe@MoS is obtained 2 SiCN precursor ceramic composite wave-absorbing material.
Comparative example 1
Step 1: preparation of Fe 3 O 4 Nanoparticles: 10mg of FeCl is taken 3 ·6H 2 O is dissolved in glycol and is subjected to ultrasonic treatment to form transparent yellow solution, then 9mg of ammonium acetate is added into the transparent yellow solution and is subjected to continuous ultrasonic treatment for 1h, then the transparent yellow solution is transferred into a stainless steel autoclave with a tetrafluoroethylene lining, and is heated for 8h at the temperature of 200 ℃ to obtain black precipitate, and then the black precipitate is subjected to centrifugal washing by ethanol for three times and is dried in vacuum at the temperature of 60 ℃ to obtain hollow Fe 3 O 4 And (3) nanoparticles.
Step 2: preparation of Fe@MoS 2 A complex: 10mg (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Dissolving O molybdenum salt and 60mg of thiourea in deionized water, magnetically stirring until the O molybdenum salt and the thiourea are completely dissolved, and weighing 5mg of hollow Fe 3 O 4 Stirring nano particles in a solution, placing the solution in an ultrasonic cleaner for ultrasonic treatment for 15min after stirring by a glass rod until the solution is black turbid liquid, transferring the liquid into a polytetrafluoroethylene lining of a reaction kettle, heating the reaction kettle to 220 ℃, preserving heat for 12h to perform hydrothermal reaction to obtain a precipitate product, washing the product with absolute ethyl alcohol for three times, drying and grinding to obtain Fe@MoS 2 A complex.
Comparative example 2
Adding 100mg of polycarbosilane and 10mg of diisopropyl peroxide into a reaction kettle, adding 4mg of methacrylic acid for full dissolution, heating to 300 ℃ at a heating rate of 5 ℃/min after full dissolution, preserving heat for 4 hours to complete a crosslinking curing reaction to obtain a cured block, putting the block material into a vibration ball mill for ball milling for 1 hour, sieving with a 200-mesh sieve to obtain powder with a particle size of about 74 mu m, pressing the powder into a blank body, performing cold isostatic pressing for 3 minutes under 180MPa, and finally sintering the pressed material at a high temperature under a nitrogen atmosphere, wherein the sintering temperature is 1300 ℃ and the sintering time is 1 hour to finally obtain the SiCN precursor ceramic material.
The electromagnetic parameters of the sample are tested by a coaxial transmission reflection method, the testing instrument is an Agilent-N5244A vector network analyzer, and the testing frequency range is 2GHz-18GHz. Weighing a sample with certain mass, fully grinding, sieving with a 100-mesh sieve, dissolving the sample and paraffin in n-hexane according to the mass ratio of 30:70, adding a small amount of solvent after ultrasonic treatment for 30min, repeating the steps for three times, fully fusing the sample and the paraffin, standing and solidifying, and then pressing in a mould to form a sample model with concentric rings with the outer diameter of 7mm, the inner diameter of 3.04mm and the thickness of 2 mm. Test mode selection coaxial method test, test results are shown in the following table.
According to the data in the table, the sample prepared in the example 1 has excellent electromagnetic wave absorption characteristics, the reflectivity is-25.63 dB, the effective absorption bandwidth is 7.56GHz, and compared with the samples in the comparative examples 1 and 2, the sample has strong wave absorption performance and wide wave absorption bandwidth, which shows that the three-dimensional conductive network structure, the interface polarization effect and the magnetic performance endow the composite material with good resistance type loss and magnetic loss performance, the impedance matching performance of the composite material is enhanced under the synergistic effect, and the excellent wave absorption effect is shown.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (9)
1. Fe@MoS 2 The preparation method of the SiCN precursor ceramic composite wave-absorbing material is characterized by comprising the following preparation processes: step 1: preparation of hollow Fe by hydrothermal method 3 O 4 A nanoparticle; step 2: in-situ precipitation reaction for preparing Fe@MoS 2 A complex; step 3: precursor conversion method for preparing Fe@MoS 2 SiCN precursor ceramic composite wave-absorbing material.
2. Fe@mos according to claim 1 2 The preparation method of the SiCN precursor ceramic composite wave-absorbing material is characterized in that the step 1 hydrothermal method is used for preparing hollow Fe 3 O 4 The specific process of the nano particle is as follows: feCl is added 3 ·6H 2 Dissolving O in glycol and performing ultrasonic treatment to form transparent yellow solution, adding ammonium acetate into the transparent yellow solution and performing continuous ultrasonic treatment for 1h, transferring the transparent yellow solution into a stainless steel autoclave with a tetrafluoroethylene lining, heating at 200 ℃ for 8h to obtain black precipitate, performing ethanol centrifugal washing for three times, and performing vacuum drying at 60 ℃ to obtain hollow Fe 3 O 4 A nanoparticle; the step 2 prepares Fe@MoS 2 The specific process of the compound is as follows: weighing molybdenum salt and thiourea, dissolving in deionized water, magnetically stirring until the molybdenum salt and thiourea are completely dissolved, and then weighing hollow Fe 3 O 4 Stirring the nano particles in a solution, placing the solution in an ultrasonic cleaner after stirring by using a glass rod until the solution is black turbid liquid, transferring the liquid into a polytetrafluoroethylene lining of a reaction kettle, obtaining a precipitate after hydrothermal reaction, washing the precipitate with absolute ethyl alcohol for three times, and then drying and grinding the precipitate; the step 3 prepares Fe@MoS 2 The specific process of the SiCN precursor ceramic composite wave-absorbing material is as follows: adding polycarbosilane and diisopropyl peroxide into a reaction kettle, adding methacrylic acid for full dissolution, and adding prepared Fe@MoS into the reaction kettle 2 After the compound is fully dissolved and crosslinked and solidified, fe@MoS is prepared through ball milling, blank pressing, cold isostatic pressing and high-temperature sintering 2 SiCN precursor ceramic composite wave-absorbing material.
3. Fe@mos according to claim 2 2 The preparation method of the SiCN precursor ceramic composite wave-absorbing material is characterized in that the FeCl 3 ·6H 2 The weight ratio of O to ammonium acetate is 10:3-10:9; the molybdenum saltThe weight ratio of the hollow Fe to the thiourea is 1:1-1:6, and the hollow Fe is prepared from the following components in percentage by weight 3 O 4 The weight ratio of the nano particles to the molybdenum salt is 1:2-1:4; the weight ratio of the polycarbosilane to the diisopropyl peroxide to the methacrylic acid is 100 (8-12) (3-5), and the polycarbosilane to the Fe@MoS 2 The weight ratio of the compound is 100:5-100:10.
4. Fe@mos according to claim 2 2 The preparation method of the SiCN precursor ceramic composite wave-absorbing material is characterized in that the molybdenum salt is sodium molybdate dihydrate (Na 2 MoO 4 ·2H 2 O), ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) one of the following.
5. Fe@mos according to claim 2 2 The preparation method of the SiCN precursor ceramic composite wave-absorbing material is characterized in that the hydrothermal reaction is carried out at the reaction temperature of 150-220 ℃ for 12-24 hours.
6. Fe@mos according to claim 2 2 The preparation method of the SiCN precursor ceramic composite wave-absorbing material is characterized in that the crosslinking and curing reaction is that the temperature is raised to 300-600 ℃ at the temperature rising rate of 5 ℃/min, and the temperature is kept for 2-4 h.
7. Fe@mos according to claim 2 2 The preparation method of the SiCN precursor ceramic composite wave-absorbing material is characterized in that the ball milling is that a sample is put into a vibration ball mill for ball milling for 1-5 hours, powder is sieved by a 100-200 mesh sieve, and the cold isostatic pressing is carried out for 3min under 180Mpa pressure.
8. Fe@mos according to claim 2 2 The preparation method of the SiCN precursor ceramic composite wave-absorbing material is characterized in that the high-temperature sintering is carried out in an inert gas atmosphere, the sintering temperature is 1100-1400 ℃, the sintering time is 0.5-1.5 h, and the inert gas is one of nitrogen, argon, helium and neon.
9. The Fe@MoS prepared by the preparation method of any one of claims 1 to 8 2 SiCN precursor ceramic composite wave-absorbing material.
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