CN108342036B - Magnetic Mxenes polymer composite wave-absorbing material and preparation method thereof - Google Patents

Magnetic Mxenes polymer composite wave-absorbing material and preparation method thereof Download PDF

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CN108342036B
CN108342036B CN201810249523.8A CN201810249523A CN108342036B CN 108342036 B CN108342036 B CN 108342036B CN 201810249523 A CN201810249523 A CN 201810249523A CN 108342036 B CN108342036 B CN 108342036B
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mxenes
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absorbing material
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composite wave
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CN108342036A (en
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彭大瑞
陈德志
邹刃
胡志威
戢元星
龚锦华
江勋剑
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Nanchang Hangkong University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/003—Additives being defined by their diameter
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a preparation method of a magnetic Mxenes polymer composite wave-absorbing material, which comprises the following steps: adding ferric oxide and cetyl trimethyl ammonium bromide into deionized water, and performing ultrasonic preparation to obtain ferric oxide dispersion liquid modified by the cetyl trimethyl ammonium bromide; the iron oxide dispersion was added dropwise to Mxenes (Ti)3C2Txene (Ti) colloid is prepared by magnetic stirring3C2Tx)/Fe2O3Carrying out suction filtration and drying on the suspension, heating the suspension in an argon atmosphere for reaction, and naturally cooling the suspension to room temperature to prepare Mxenes (Ti)3C2Tx)/Fe3O4A nanocomposite; adding polyvinylidene fluoride and N, N-dimethylformamide, and performing ultrasonic treatment to obtain Mxenes (Ti)3C2Tx)/Fe3O4Mixing the nanometer composite material and polyvinylidene fluoride uniformly, putting the mixture into a die, hot-pressing, maintaining pressure and cooling to prepare the Mxenes (Ti)3C2Tx)/Fe3O4Filled polyvinylidene fluoride composite wave-absorbing material. The composite material prepared by the preparation method provided by the invention has the advantages of high polymer substrate content, easiness in film formation, easiness in processing, light weight and easiness in industrial production.

Description

Magnetic Mxenes polymer composite wave-absorbing material and preparation method thereof
Technical Field
The invention relates to the field of composite material preparation, in particular to a magnetic Mxenes polymer composite wave-absorbing material and a preparation method thereof.
Background
As a fourth generation fighter (american standard, fifth generation of russian standard), such as F22, fighter 20, the highlighted one of the 4S performance indexes is low detectability (commonly called "stealth") which is the hot field of modern scientific research, and depends mainly on a layer of wave-absorbing material coated on the surface of an airplane besides on the aerodynamic shape of the airplane. With the continuous progress of modern radar detection technology, higher requirements are put on wave absorbing materials. The latest requirements of the current wave-absorbing material are thin, light in weight, wide in frequency band and strong in absorption, but the traditional wave-absorbing material has the defects of large density, thick thickness, narrow frequency band and the like, and the requirements of the current wave-absorbing material are difficult to meet.
Two-dimensional transition metal carbon nitrogen compounds (MXenes) are two-dimensional materials which are discovered and synthesized only in recent years and are synthesized after MAX-phase ceramics are used as precursors and an A element is selectively etched, and the MXenes has typical graphene-like materials and has the advantages of rich surface functional groups, strong conductivity, easiness in film formation and the like. MXenes can convert the energy of electromagnetic waves into heat energy, has wide application prospect in the field of wave-absorbing materials, and is a general name of a class of materials, wherein Ti is3C2Tx is the most widely studied one. Ti3C2The composite material of Tx and sodium alginate has shown excellent electromagnetic shielding performance, which is published in Science in 2016, but MXenes sheets are easy to agglomerate among layers, which limits the performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a magnetic Mxenes polymer composite wave-absorbing material in a first aspect, which comprises the following steps:
s1: adding powdered iron oxide and cetyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment to uniformly disperse the iron oxide in the deionized water to prepare a cetyl trimethyl ammonium bromide modified iron oxide dispersion liquid;
s2: the iron oxide dispersion liquid prepared in step S1 was added dropwise to Mxenes (Ti)3C2Txene (Ti) colloid is prepared by magnetic stirring3C2Tx)/ Fe2O3The suspension is filtered and dried by an inorganic filter membrane to obtain Mxenes (Ti)3C2Tx)/Fe2O3Precipitating;
s3: mxenes (Ti) prepared in step S23C2Tx)/Fe2O3The precipitate is firstly heated and reacted in the argon atmosphere, and then is naturally cooled to the room temperature to prepare Mxenes (Ti)3C2Tx)/Fe3O4A nanocomposite;
s4: the resulting Mxenes (Ti) is prepared at step S33C2Tx)/Fe3O4Adding N, N-dimethylformamide into the mixture of the nano composite material and the polyvinylidene fluoride, and performing ultrasonic treatment to obtain Mxenes (Ti)3C2Tx)/Fe3O4Uniformly mixing the nano composite material and polyvinylidene fluoride;
s5: mixing the uniformly mixed Mxenes (Ti) in step S43C2Tx)/Fe3O4The nanometer composite material and the polyvinylidene fluoride material are put into a mould to be hot-pressed and then pressure-maintaining cooled to prepare Mxenes (Ti)3C2Tx)/Fe3O4Filled polyvinylidene fluoride composite wave-absorbing material.
Wherein the iron oxide is α -Fe2O3α -Fe as described2O3The preparation method comprises the following steps: adding 2.73g ferric trichloride hexahydrate and 2g urea into 100mL deionized water, heating in water bath at 90 ℃ for 5h, simultaneously magnetically stirring, centrifugally collecting precipitate generated by the reaction after the reaction is completed, washing by deionization, drying at 60 ℃ for 12h to prepare iron oxyhydroxide, heating the iron oxyhydroxide to 450 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and then, drying for 12h to obtain the iron oxyhydroxideNaturally cooling to room temperature to prepare α -Fe2O3。
Wherein the mass ratio of the ferric oxide to the hexadecyl trimethyl ammonium bromide is 1: 10-1: 30.
Preferably, the mass ratio of the ferric oxide to the hexadecyl trimethyl ammonium bromide is 1:15, 1:20 and 1: 25.
Wherein the solid-to-liquid ratio of the ferric oxide to the deionized water is 10: 100-200 mg/mL.
Preferably, the solid-to-liquid ratio of the iron oxide to the deionized water is 10:120mg/mL, 10:140mg/mL, 10:160mg/mL, 10:180 mg/mL.
Wherein said iron oxide and said Mxenes (Ti)3C2Tx) is 15: 85-85: 85.
Preferably, said iron oxide and said Mxenes (Ti)3C2Tx) in a mass ratio of 20:85, 30:85, 40:85, 50:85, 60:85, 70:85, 80: 85.
Wherein, the Mxenes (Ti)3C2Tx)/Fe3O4The mass percentage of the composite material to the polyvinylidene fluoride is 5-20% to 80-95%.
Preferably, said Mxenes (Ti)3C2Tx)/Fe3O4The composite material and the polyvinylidene fluoride comprise, by mass, 6% to 94%, 7% to 93%, 8% to 92%, 9% to 91%, 10% to 90%, 11% to 89%, 12% to 88%, 13% to 87%, 14% to 86%, 15% to 85%, 16% to 84%, 17% to 83%, 18% to 82%, and 19% to 81%.
In the step S3, the heating reaction is carried out under the conditions of heating to 350-500 ℃ at a heating rate of 3-7 ℃/min and keeping the temperature for 15-45 min.
Preferably, the heating reaction is carried out under the conditions of heating to 400-450 ℃ at the heating rate of 4-5 ℃/min and keeping the temperature for 20-35 min.
In the step S4, the hot pressing temperature is 200-240 ℃, the pressure is 10-20 MPa, and the time is 2-6 h.
Preferably, the hot pressing temperature is 210-230 ℃, the pressure is 12-18 MPa, and the time is 2.5-4.5 h.
In a second aspect, the invention provides a magnetic article MXenes polymer composite wave-absorbing material, wherein Mxenes (Ti) in the composite wave-absorbing material3C2Tx)/Fe3O4The mass percent of the nano composite material is 5% -20%, and the Mxenes (Ti) is3C2Tx)/Fe3O4Fe in nanocomposites3O4The mass percent of the Mxenes is 14.6% -49.8%, and the Mxenes (Ti)3C2Tx) is a few or a single layer of four or less layers, the Fe3O4Is polyhedral and has a particle diameter of 200 to 300 nm.
The invention has the beneficial effects that:
the preparation method of the magnetic Mxenes polymer composite wave-absorbing material provided by the invention is prepared by simple wet chemistry and heat treatment, and has the following advantages:
(1) mxenes (Ti) of high conductivity3C2Tx) and magnetic Fe3O4Compounding inhibits Mxenes (Ti)3C2Tx) stacking of slices;
(2) α -Fe with the surfactant cetyl trimethyl ammonium bromide2O3The nanoparticles are homogeneously dispersed and mixed with Mxenes (Ti)3C2Tx) lamellae are uniformly contacted;
(3) α -Fe by cracking residual hexadecyl trimethyl ammonium bromide at high temperature to generate C2O3Reduction to Fe3O4。
(4) The composite material has the advantages of high polymer substrate content, easy film formation, easy processing, light weight and easy industrial production.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it should be obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts;
FIG. 1 shows α -Fe prepared by the present invention2O3SEM picture of (1);
FIG. 2 shows Mxenes (Ti) prepared in example 1 of the present invention3C2Tx)/Fe3O4SEM image of the nanocomposite.
Detailed Description
The following is a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention.
Example 1
The invention provides a preparation method of a magnetic Mxenes polymer composite wave-absorbing material, which comprises the following steps:
s1: adding 20mg of powdered iron oxide and 200mg of hexadecyl trimethyl ammonium bromide into 200mL of deionized water, and performing ultrasonic treatment to uniformly disperse the iron oxide in the deionized water to prepare an iron oxide dispersion liquid modified by the hexadecyl trimethyl ammonium bromide;
s2: the iron oxide dispersion prepared in step S1 was added dropwise to 800mL of Mxenes (Ti) having a concentration of 0.1mg/mL3C2Tx) colloid, magnetically stirring for 24h to prepare Mxenes (Ti)3C2Tx)/ Fe2O3The suspension was then filtered through a 0.22 μm pore size inorganic filter to obtain Mxenes (Ti)3C2Tx)/ Fe2O3The suspension is filtered with suction and dried at 60 ℃ for 12h to give Mxenes (Ti)3C2Tx)/Fe2O3Precipitating;
s3: mxenes (Ti) prepared in step S23C2Tx)/Fe2O3Placing the precipitate in a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, preserving the heat for 30min, and naturally cooling to room temperature to obtain black powder Mxenes (Ti)3C2Tx)/Fe3O4A nanocomposite;
s4: mxenes (Ti) prepared in step S3 was weighed3C2Tx)/Fe3O40.05g of nano composite material and 0.95g of polyvinylidene fluoride are addedSolvent N, N-dimethylformamide, ultrasonic treating for 1h to obtain Mxenes (Ti)3C2Tx)/Fe3O4Uniformly mixing the nano composite material and polyvinylidene fluoride, and naturally airing;
s5: mixing the uniformly mixed Mxenes (Ti) in step S43C2Tx)/Fe3O4Loading the nano composite material and polyvinylidene fluoride material into a mold, placing on a hot press, pressing at 200 deg.C and 10MPa for 4 hr, and cooling under constant pressure to obtain Mxenes (Ti)3C2Tx)/Fe3O4Filled polyvinylidene fluoride composite wave-absorbing material.
The iron oxide is α -Fe2O3The preparation method comprises the following steps:
adding 2.73g of ferric trichloride hexahydrate and 2g of urea into 100mL of deionized water, heating in a water bath for 5h at 90 ℃, simultaneously performing magnetic stirring, centrifugally collecting precipitates generated in the reaction after the reaction is completed, washing by deionization, drying for 12h at the temperature of 60 ℃ to prepare iron oxyhydroxide, finally heating the iron oxyhydroxide to 450 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 2h, naturally cooling to room temperature to prepare α -Fe2O3。
The magnetic Mxenes polymer composite wave-absorbing material prepared by the embodiment contains Mxenes (Ti)3C2Tx)/Fe3O4The mass percent of the nano composite material is 5 percent, and Mxenes (Ti) in the composite wave-absorbing material3C2Tx) is a few or a single layer of four or less layers, Fe3O4Is polyhedral and has a particle diameter of 200 to 300 nm.
As can be seen from FIGS. 1 and 2, α -Fe was obtained in example 12O3The nano-particles are in an ellipsoidal shape and are bonded to d-Ti3C2After Tx recombination and heat treatment, d-Ti3C2Tx lamellae are distributed at α -Fe2O3On the surface of the nanoparticles and α -Fe before and after the heat treatment2O3Has no obvious change in shape and is still ellipsoidal. This structure improves the electrical conductivity of the composite material and avoidsBy Ti3C2The stacking of Tx sheets improves the wave absorbing property, cetyl trimethyl ammonium bromide is carbonized during the heat treatment process, and the generated carbon is α -Fe2O3Reduction to Fe3O4，Fe3O4Is a strong magnetic substance, thus greatly improving the magnetism of the material and being beneficial to improving the wave absorption performance.
Example 2
The invention provides a preparation method of a magnetic Mxenes polymer composite wave-absorbing material, which comprises the following steps:
s1: adding 30mg of powdered iron oxide and 300mg of hexadecyl trimethyl ammonium bromide into 400mL of deionized water, and performing ultrasonic treatment to uniformly disperse the iron oxide in the deionized water to prepare an iron oxide dispersion liquid modified by the hexadecyl trimethyl ammonium bromide;
s2: the iron oxide dispersion prepared in step S1 was added dropwise to 700mL of Mxenes (Ti) having a concentration of 0.1mg/mL3C2Tx) colloid, magnetically stirring for 24h to prepare Mxenes (Ti)3C2Tx)/ Fe2O3The suspension was then filtered through a 0.22 μm pore size inorganic filter to obtain Mxenes (Ti)3C2Tx)/ Fe2O3The suspension is filtered with suction and dried at 60 ℃ for 12h to give Mxenes (Ti)3C2Tx)/Fe2O3Precipitating;
s3: mxenes (Ti) prepared in step S23C2Tx)/Fe2O3Placing the precipitate in a tube furnace, heating to 450 deg.C at a heating rate of 4 deg.C/min in argon atmosphere, maintaining the temperature for 20min, and naturally cooling to room temperature to obtain black powder Mxenes (Ti)3C2Tx)/Fe3O4A nanocomposite;
s4: mxenes (Ti) prepared in step S3 was weighed3C2Tx)/Fe3O4Adding 0.1g of nano composite material and 0.9g of polyvinylidene fluoride into N, N-dimethylformamide serving as a solvent, and performing ultrasonic treatment for 1 hour to obtain Mxenes (Ti)3C2Tx)/Fe3O4Nanocomposite materialMixing with polyvinylidene fluoride uniformly, and naturally drying;
s5: mixing the uniformly mixed Mxenes (Ti) in step S43C2Tx)/Fe3O4Placing the nano composite material and polyvinylidene fluoride material into a mould, placing on a hot press, pressing for 3h at the temperature of 210 ℃ and the pressure of 15MPa, and then maintaining the pressure and cooling to prepare the Mxenes (Ti)3C2Tx)/Fe3O4Filled polyvinylidene fluoride composite wave-absorbing material.
The iron oxide is α -Fe2O3The preparation method comprises the following steps:
adding 2.73g of ferric trichloride hexahydrate and 2g of urea into 100mL of deionized water, heating in a water bath for 5h at 90 ℃, simultaneously performing magnetic stirring, centrifugally collecting precipitates generated in the reaction after the reaction is completed, washing by deionization, drying for 12h at the temperature of 60 ℃ to prepare iron oxyhydroxide, finally heating the iron oxyhydroxide to 450 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 2h, naturally cooling to room temperature to prepare α -Fe2O3。
The magnetic Mxenes polymer composite wave-absorbing material prepared by the embodiment contains Mxenes (Ti)3C2Tx)/Fe3O4The mass percentage of the nano composite material is 10 percent, and Mxenes (Ti) in the composite wave-absorbing material3C2Tx) is a few or a single layer of four or less layers, Fe3O4Is polyhedral and has a particle diameter of 200 to 300 nm.
Example 3
The invention provides a preparation method of a magnetic Mxenes polymer composite wave-absorbing material, which comprises the following steps:
s1: adding 40mg of powdered iron oxide and 400mg of hexadecyl trimethyl ammonium bromide into 500mL of deionized water, and performing ultrasonic treatment to uniformly disperse the iron oxide in the deionized water to prepare an iron oxide dispersion liquid modified by the hexadecyl trimethyl ammonium bromide;
s2: the iron oxide dispersion prepared in step S1 was added dropwise to 600mL of Mxenes (Ti) having a concentration of 0.1mg/mL3C2Tx) glueIn vivo, magnetic stirring was carried out for 24h to prepare Mxenes (Ti)3C2Tx)/ Fe2O3The suspension was then filtered through a 0.22 μm pore size inorganic filter to obtain Mxenes (Ti)3C2Tx)/ Fe2O3The suspension is filtered with suction and dried at 60 ℃ for 12h to give Mxenes (Ti)3C2Tx)/Fe2O3Precipitating;
s3: mxenes (Ti) prepared in step S23C2Tx)/Fe2O3Placing the precipitate in a tube furnace, heating to 450 deg.C at a heating rate of 6 deg.C/min in argon atmosphere, maintaining the temperature for 40min, and naturally cooling to room temperature to obtain black powder Mxenes (Ti)3C2Tx)/Fe3O4A nanocomposite;
s4: mxenes (Ti) prepared in step S3 was weighed3C2Tx)/Fe3O4Adding 0.15g of nano composite material and 0.85g of polyvinylidene fluoride into N, N-dimethylformamide serving as a solvent, and performing ultrasonic treatment for 1 hour to obtain Mxenes (Ti)3C2Tx)/Fe3O4Uniformly mixing the nano composite material and polyvinylidene fluoride, and naturally airing;
s5: mixing the uniformly mixed Mxenes (Ti) in step S43C2Tx)/Fe3O4Placing the nano composite material and polyvinylidene fluoride material into a mould, placing on a hot press, pressing for 4.5h at 220 ℃ and 12MPa, and then maintaining the pressure and cooling to obtain the Mxenes (Ti)3C2Tx)/Fe3O4Filled polyvinylidene fluoride composite wave-absorbing material.
The iron oxide is α -Fe2O3The preparation method comprises the following steps:
adding 2.73g ferric trichloride hexahydrate and 2g urea into 100mL deionized water, heating in water bath at 90 ℃ for 5h, simultaneously magnetically stirring, centrifugally collecting precipitate generated by the reaction after the reaction is completed, washing by deionization, drying at 60 ℃ for 12h to prepare iron oxyhydroxide, heating the iron oxyhydroxide to 450 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and naturally coolingCooling to room temperature to prepare α -Fe2O3。
The magnetic Mxenes polymer composite wave-absorbing material prepared by the embodiment contains Mxenes (Ti)3C2Tx)/Fe3O4The mass percentage of the nano composite material is 15 percent, and Mxenes (Ti) in the composite wave-absorbing material3C2Tx) is a few or a single layer of four or less layers, Fe3O4Is polyhedral and has a particle diameter of 200 to 300 nm.
Example 4
The invention provides a preparation method of a magnetic Mxenes polymer composite wave-absorbing material, which comprises the following steps:
s1: adding 20mg of powdered iron oxide and 300mg of hexadecyl trimethyl ammonium bromide into 300mL of deionized water, and performing ultrasonic treatment to uniformly disperse the iron oxide in the deionized water to prepare an iron oxide dispersion liquid modified by the hexadecyl trimethyl ammonium bromide;
s2: the iron oxide dispersion prepared in step S1 was added dropwise to 500mL of Mxenes (Ti) at a concentration of 0.1mg/mL3C2Tx) colloid, magnetically stirring for 24h to prepare Mxenes (Ti)3C2Tx)/ Fe2O3The suspension was then filtered through a 0.22 μm pore size inorganic filter to obtain Mxenes (Ti)3C2Tx)/ Fe2O3The suspension is filtered with suction and dried at 60 ℃ for 12h to give Mxenes (Ti)3C2Tx)/Fe2O3Precipitating;
s3: mxenes (Ti) prepared in step S23C2Tx)/Fe2O3Placing the precipitate in a tube furnace, heating to 420 deg.C at a heating rate of 5 deg.C/min in argon atmosphere, maintaining the temperature for 25min, and naturally cooling to room temperature to obtain black powder Mxenes (Ti)3C2Tx)/Fe3O4A nanocomposite;
s4: mxenes (Ti) prepared in step S3 was weighed3C2Tx)/Fe3O40.2g of nano composite material and 0.8g of polyvinylidene fluoride, adding solvent N, N-dimethyl methylAmide, sonicate for 1h, to Mxenes (Ti)3C2Tx)/Fe3O4Uniformly mixing the nano composite material and polyvinylidene fluoride, and naturally airing;
s5: mixing the uniformly mixed Mxenes (Ti) in step S43C2Tx)/Fe3O4Placing the nano composite material and polyvinylidene fluoride material into a mould, placing the mould on a hot press, mould-pressing for 5.5h at the temperature of 225 ℃ and the pressure of 18MPa, and then maintaining the pressure and cooling to prepare the Mxenes (Ti)3C2Tx)/Fe3O4Filled polyvinylidene fluoride composite wave-absorbing material.
The iron oxide is α -Fe2O3The preparation method comprises the following steps:
adding 2.73g of ferric trichloride hexahydrate and 2g of urea into 100mL of deionized water, heating in a water bath for 5h at 90 ℃, simultaneously performing magnetic stirring, centrifugally collecting precipitates generated in the reaction after the reaction is completed, washing by deionization, drying for 12h at the temperature of 60 ℃ to prepare iron oxyhydroxide, finally heating the iron oxyhydroxide to 450 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 2h, naturally cooling to room temperature to prepare α -Fe2O3。
The magnetic Mxenes polymer composite wave-absorbing material prepared by the embodiment contains Mxenes (Ti)3C2Tx)/Fe3O4The mass percentage of the nano composite material is 20 percent, and Mxenes (Ti) in the composite wave-absorbing material3C2Tx) is a few or a single layer of four or less layers, Fe3O4Is polyhedral and has a particle diameter of 200 to 300 nm.
Example 5
The invention provides a preparation method of a magnetic Mxenes polymer composite wave-absorbing material, which comprises the following steps:
s1: adding 10mg of powdered iron oxide and 200mg of hexadecyl trimethyl ammonium bromide into 200mL of deionized water, and performing ultrasonic treatment to uniformly disperse the iron oxide in the deionized water to prepare an iron oxide dispersion liquid modified by the hexadecyl trimethyl ammonium bromide;
s2: manufactured by the step S1The iron oxide dispersion thus obtained was added dropwise to 300mL of Mxenes (Ti) having a concentration of 0.1mg/mL3C2Tx) colloid, magnetically stirring for 24h to prepare Mxenes (Ti)3C2Tx)/ Fe2O3The suspension was then filtered through a 0.22 μm pore size inorganic filter to obtain Mxenes (Ti)3C2Tx)/ Fe2O3The suspension is filtered with suction and dried at 60 ℃ for 12h to give Mxenes (Ti)3C2Tx)/Fe2O3Precipitating;
s3: mxenes (Ti) prepared in step S23C2Tx)/Fe2O3Placing the precipitate in a tube furnace, heating to 380 deg.C at a heating rate of 3 deg.C/min in argon atmosphere, maintaining the temperature for 25min, and naturally cooling to room temperature to obtain black powder Mxenes (Ti)3C2Tx)/Fe3O4A nanocomposite;
s4: mxenes (Ti) prepared in step S3 was weighed3C2Tx)/Fe3O4Adding 0.1g of nano composite material and 0.9g of polyvinylidene fluoride into N, N-dimethylformamide serving as a solvent, and performing ultrasonic treatment for 1 hour to obtain Mxenes (Ti)3C2Tx)/Fe3O4Uniformly mixing the nano composite material and polyvinylidene fluoride, and naturally airing;
s5: mixing the uniformly mixed Mxenes (Ti) in step S43C2Tx)/Fe3O4Placing the nano composite material and polyvinylidene fluoride material into a mould, placing on a hot press, pressing for 5h at 230 ℃ and 15MPa, and then maintaining the pressure and cooling to obtain the Mxenes (Ti)3C2Tx)/Fe3O4Filled polyvinylidene fluoride composite wave-absorbing material.
The iron oxide is α -Fe2O3The preparation method comprises the following steps:
adding 2.73g ferric trichloride hexahydrate and 2g urea into 100mL deionized water, heating in water bath at 90 ℃ for 5h, simultaneously magnetically stirring, centrifugally collecting precipitate generated by the reaction after the reaction is completed, washing by deionization, and drying at 60 ℃ for 12h to prepare the iron oxyhydroxideFinally, heating the hydroxyl ferric oxide to 450 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and naturally cooling to room temperature to prepare α -Fe2O3。
The magnetic Mxenes polymer composite wave-absorbing material prepared by the embodiment contains Mxenes (Ti)3C2Tx)/Fe3O4The mass percentage of the nano composite material is 10 percent, and Mxenes (Ti) in the composite wave-absorbing material3C2Tx) is a few or a single layer of four or less layers, Fe3O4Is polyhedral and has a particle diameter of 200 to 300 nm.
Comparative test
To verify the conventional iron oxide with α -Fe prepared according to the present invention2O3The invention also provides a comparative test for the influence on the wave absorption performance of the magnetic Mxenes polymer composite wave-absorbing material, controls other process parameters to be unchanged with reference to the examples 1-5, and adopts conventional iron oxide to replace α -Fe prepared by the invention2O3And the wave-absorbing performance of the finally prepared magnetic Mxenes polymer composite wave-absorbing material is obviously lower than that of the magnetic Mxenes polymer composite wave-absorbing material prepared in the embodiments 1-5.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the spirit of the present invention, and these changes and modifications are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The preparation method of the magnetic MXenes polymer composite wave-absorbing material is characterized by comprising the following steps of:
s1: adding powdered iron oxide and cetyl trimethyl ammonium bromide into deionized water, and performing ultrasonic treatment to uniformly disperse the iron oxide in the deionized water to prepare a cetyl trimethyl ammonium bromide modified iron oxide dispersion liquid;
s2: adding dropwise the iron oxide dispersion prepared in step S1 to Ti3C2TxIn the colloid, Ti is prepared by magnetic stirring3C2Tx/Fe2O3The suspension is filtered and dried by an inorganic filter membrane to obtain Ti3C2Tx/Fe2O3Precipitating;
s3: ti prepared in the step S23C2Tx/Fe2O3The precipitate is firstly heated and reacted in argon atmosphere, and then is naturally cooled to room temperature to prepare Ti3C2Tx/Fe3O4A nanocomposite;
s4: ti prepared in step S33C2Tx/Fe3O4Adding N, N-dimethylformamide into the mixture of the nano composite material and the polyvinylidene fluoride, and performing ultrasonic treatment to obtain Ti3C2Tx/Fe3O4Uniformly mixing the nano composite material and polyvinylidene fluoride;
s5: mixing Ti uniformly in step S43C2Tx/Fe3O4The nano composite material and the polyvinylidene fluoride material are filled into a die to be hot-pressed, and then pressure maintaining and cooling are carried out to prepare the Ti3C2Tx/Fe3O4Filled polyvinylidene fluoride composite wave-absorbing material;
the iron oxide is α -Fe2O3。
2. The method for preparing the magnetic MXenes polymer composite wave-absorbing material of claim 1, wherein α -Fe2O3The preparation method comprises the following steps: adding 2.73g ferric trichloride hexahydrate and 2g urea into 100mL deionized water, heating in water bath at 90 ℃ for 5h, magnetically stirring, centrifugally collecting precipitate generated by the reaction after the reaction is completed, washing with deionized water, drying at 60 ℃ for 12h to prepare ferric hydroxide, and finally cooling the ferric hydroxide at 5 DEG CHeating to 450 ℃ at a heating rate of/min, preserving heat for 2h, and naturally cooling to room temperature to prepare α -Fe2O3。
3. The preparation method of the magnetic MXenes polymer composite wave-absorbing material according to claim 1 or 2, wherein the preparation method comprises the following steps: the mass ratio of the ferric oxide to the hexadecyl trimethyl ammonium bromide is 1: 10-1: 30.
4. The preparation method of the magnetic MXenes polymer composite wave-absorbing material according to claim 1 or 2, wherein the preparation method comprises the following steps: the solid-liquid ratio of the ferric oxide to the deionized water is 10: 100-200 mg/mL.
5. The preparation method of the magnetic MXenes polymer composite wave-absorbing material according to claim 1 or 2, wherein the preparation method comprises the following steps: the iron oxide and the Ti3C2TxThe mass ratio of (A) to (B) is 15: 85-85: 85.
6. The preparation method of the magnetic MXenes polymer composite wave-absorbing material according to claim 1 or 2, wherein the preparation method comprises the following steps: the Ti3C2Tx/Fe3O4The mass percentage of the composite material to the polyvinylidene fluoride is 5-20% to 80-95%.
7. The preparation method of the magnetic MXenes polymer composite wave-absorbing material according to claim 1 or 2, wherein the preparation method comprises the following steps: in the step S3, the heating reaction conditions are that the temperature is raised to 350-500 ℃ at a heating rate of 3-7 ℃/min, and the temperature is kept for 15-45 min.
8. The preparation method of the magnetic MXenes polymer composite wave-absorbing material according to claim 1 or 2, wherein the preparation method comprises the following steps: in the step S5, the hot pressing temperature is 200-240 ℃, the pressure is 10-20 MPa, and the time is 2-6 h.
9. Magnetic MXenesThe polymer composite wave-absorbing material is characterized in that: the composite wave-absorbing material is prepared by the method according to any one of claims 1 to 8, and Ti in the composite wave-absorbing material3C2Tx/Fe3O4The mass percent of the nano composite material is 5% -20%, and the Ti is3C2Tx/Fe3O4Fe in nanocomposites3O4The mass percentage of the component (A) is 14.6-49.8%.
10. The magnetic MXenes polymer composite wave-absorbing material of claim 9, wherein: ti in the composite wave-absorbing material3C2TxIs a multilayer or single layer of four or less layers, the Fe3O4Is polyhedral and has a particle diameter of 200 to 300 nm.
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