CN114874751B - Gradient heating fold MXene/TiO2Preparation method of paraffin and electromagnetic shielding application thereof - Google Patents
Gradient heating fold MXene/TiO2Preparation method of paraffin and electromagnetic shielding application thereof Download PDFInfo
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- 239000012188 paraffin wax Substances 0.000 title claims abstract description 67
- 238000010438 heat treatment Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims description 30
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 86
- 239000000463 material Substances 0.000 claims abstract description 63
- 239000004202 carbamide Substances 0.000 claims abstract description 61
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000004108 freeze drying Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000005530 etching Methods 0.000 claims abstract description 9
- 239000002135 nanosheet Substances 0.000 claims description 25
- 230000037303 wrinkles Effects 0.000 claims description 18
- -1 urea compound Chemical class 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 24
- 238000003756 stirring Methods 0.000 abstract description 17
- 239000006228 supernatant Substances 0.000 abstract description 16
- 229910052786 argon Inorganic materials 0.000 abstract description 12
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005119 centrifugation Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 9
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- 238000005516 engineering process Methods 0.000 description 7
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241001214257 Mene Species 0.000 description 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000012535 impurity Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the field of electromagnetic shielding materials, and discloses a preparation method of gradient heating pleated MXene/TiO 2/paraffin and an electromagnetic shielding application thereof. The preparation method of the invention comprises the following steps: step 1: adding Ti 3AlC2 into LiF and HCl solution, stirring and etching, centrifuging and washing until the pH of the supernatant is more than 6, and obtaining multi-layer MXene; step 2: centrifuging the multi-layer MXene obtained in the step 1 by ultrasonic, and freeze-drying the supernatant to obtain a few-layer MXene; step 3: mixing and stirring a few-layer MXene and urea in a mass ratio of 1:5, and freeze-drying to obtain the folded MXene/urea; step 4: placing the folded MXene/urea treated in the step 3 into a tubular furnace for gradient heating, firstly heating to 200 ℃ under the atmosphere of air, partially oxidizing to obtain folded MXene/TiO 2/urea, keeping the temperature for 10-30min, continuously heating to 500-700 ℃ under the atmosphere of argon, keeping the temperature for 2h, cooling to room temperature, taking out the folded MXene/TiO 2 of the sample, mixing with paraffin to prepare the MXene/TiO 2/paraffin material, and applying the material to electromagnetic shielding. The invention can obviously improve the electromagnetic shielding performance of the MXene material.
Description
Technical Field
The invention relates to the field of electromagnetic shielding materials, in particular to a method for designing an electromagnetic shielding material which can be used in the field of electromagnetic shielding, wherein urea is used for inducing MXene to form a fold morphology, then the fold MXene/TiO 2 is prepared by gradient heating, and finally the electromagnetic shielding performance of the MXene material mixed with paraffin is obviously improved.
Background
The rapid development of communication technology and electronic industry brings great convenience to human life, but high-density electromagnetic waves easily interfere with the normal operation of modern electronic equipment, and meanwhile, people are directly exposed to increasing electromagnetic wave radiation, so that serious health hidden trouble is brought. In recent years, electromagnetic waves have become a source of yet another large pollution besides water, atmosphere, noise. Therefore, developing and designing efficient electromagnetic shielding materials to ensure normal electronic communication and human health becomes a current research hotspot. Metals and alloys can exhibit excellent electromagnetic shielding effectiveness as conventional electromagnetic shielding materials due to their high electrical conductivity. However, the characteristics of easy corrosion, high density, difficult processing and the like severely limit the application of the composite material. As a novel high-performance electromagnetic shielding material, the MXene-based composite material has been widely focused on solving the electromagnetic wave pollution because of the advantages of light weight, easy processing, strong electric conductivity and the like.
There are two main approaches to achieve higher electromagnetic shielding effectiveness: the first method is to prepare an electromagnetic shielding material based on reflection. When electromagnetic waves are incident on the surface, most of the electromagnetic waves are reflected back into the air due to the strong interaction between the electromagnetic field and surface electrons, so that the electromagnetic shielding effect is achieved; the second method is to prepare an electromagnetic shielding material based on absorption. For a material which has a general conductivity but contains a large number of defects such as interfaces and the like, when most of electromagnetic waves which cannot be reflected enter the material due to poor conductivity of the material, the centers of positive charges and negative charges cannot be overlapped due to uneven distribution of peripheral electrons of surface functional groups, impurity atoms and the like under the action of an electromagnetic field, and a dipole is generated, and the phenomenon is called dipole polarization. In the electromagnetic field which alternately goes forward and backward, the positions of the positive charge part and the negative charge part of the dipole are changed continuously, as the frequency of the electromagnetic field increases, the movement of the dipole cannot keep up with the change of the electromagnetic field, and the force of the electromagnetic field pushes the dipole to move, so that the energy of the electromagnetic field is converted into heat energy to be dissipated, and the phenomenon is called relaxation caused by polarization of the dipole. For the interface contained in the composite material, a large amount of charges are accumulated at two sides of the interface due to different conductivities, so that interface polarization is generated, and when the frequency of the electromagnetic field is increased, relaxation caused by the interface polarization is also generated to attenuate electromagnetic waves.
Untreated MXene is an electromagnetic shielding material based on reflection, has a smooth surface and strong electrical conductivity, and reflects a large amount of electromagnetic waves into the air when the electromagnetic waves are incident on the surface of a concentric annular block of MXene and paraffin. However, at the same filling rate, the specific surface area of MXene is smaller and the electromagnetic wave tends to contact the paraffin surface instead of the MXene surface. Paraffin is a typical wave-transparent material, and incident electromagnetic waves directly pass through the paraffin, so that the shielding effect cannot be achieved. Thus, untreated MXene and paraffin composites exhibit poor electromagnetic shielding effectiveness. Meanwhile, electromagnetic waves injected into the interior of the material are difficult to be absorbed due to defects such as lack of interfaces, which limits further improvement of electromagnetic shielding performance thereof. In recent years, therefore, the use of MXene in combination with other substances to improve the electromagnetic shielding performance of composite materials has been a hot spot of research at home and abroad.
Qin Wenfeng et al (Ti 3C2Tx film preparation and electromagnetic shielding performance research [ J ]. Science and engineering, 2021,21 (2): 486-490) prepared a Ti 3C2Tx film with high conductivity, which has an electromagnetic shielding performance of only 52.23dB at maximum.
Chinese patent document CN110672670B discloses a method of three-dimensional MXene folded sphere/ZnO composite. The method for preparing the three-dimensional MXene fold ball by treating the MXene by adopting an ultrasonic spraying method achieves the advantages of preventing aggregation and maintaining the specific surface area of the MXene to the maximum extent. The required ultrasonic atomizer is expensive and the experimental cost is high. And the MXene and ZnO are only mechanically mixed, so that the structure is unstable.
Chinese patent document CN112954991a discloses a method of metal nanowires/corrugations MXene. After dispersing the MXene powder in water, intercalation is carried out through at least 4 times of freezing-thawing operations to obtain the MXene nano-sheets with wrinkles, and then the MXene nano-sheets are added with the metal nanowire dispersion liquid for stirring and then are subjected to freezing-thawing operations to complete assembly. The method needs to firstly cool to minus 20 to minus 40 ℃ for 2 to 3 hours, then take out and put in the environment of 20 to 40 ℃ for thawing, and repeatedly circulate for at least four times. The operation is complicated, and the time cost is long. And the binding force between the metal nanowire and the MXene is poor, and the structure is easy to break.
Paper <Flexible Photodriven Actuator Based on Gradient–Paraffin-Wax-Filled Ti3C2Tx MXene Film for Bionic Robots> discloses a flexible light driven actuator based on a gradient-paraffin filled Ti 3C2Tx MXene film for use in biomimetic robots. The gradient-paraffin filling method used in the work is that an MXene film is placed on the side face of a paraffin film, the paraffin film is heated to be melted and diffused between MXene sheet layers, the paraffin-MXene film is removed within 1 second, at the moment, more paraffin is at the edge of the MXene film, less paraffin is in the middle of the film, and gradient change of paraffin filling is formed. The gradient mentioned by the method is the gradient of the diffusion degree of paraffin in the MXene film, and meanwhile, the method is difficult to accurately control the content of the paraffin gradient at different positions, so that the experimental repeatability is poor.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing the MXene material with simple process, low cost, time saving and excellent electromagnetic shielding performance. The method can overcome the defects of the prior art, and solves the problems that the prior art is complex, the production cost is high, and the sample cannot be produced on a large scale.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
In a first aspect of the invention, there is provided a method of preparing gradient heated pleated MXene/TiO 2/paraffin, comprising:
Uniformly mixing a few-layer MXene nano sheet and urea in a solvent to obtain an MXene/urea material with a wrinkle morphology;
Heating the MXene/urea material with the wrinkle morphology below 200 ℃ to obtain a wrinkle Mene/TiO 2/urea compound;
Heating the corrugated MXene/TiO 2/urea composite in an inert gas at 500-700 ℃ to obtain a gradient heated corrugated MXene/TiO 2;
And compounding the gradient heated wrinkles MXene/TiO 2 with paraffin wax to obtain the modified mineral wax.
The preparation method of the application evenly mixes the MXene powder with the paraffin matrix to prepare the concentric ring block material, the filling rate used is a fixed value, and the repeatability of the experiment is strong. Meanwhile, the specific meaning of the gradient used in the application is temperature gradient, namely, the temperature gradient is that the wrinkles MXene is heated at low temperature in air to partially oxidize the wrinkles MXene into TiO 2, and then urea which induces the morphology agent is removed by heating at high temperature in argon, and the used variables are temperature and time, so that the repeatability of the experiment is strong, and the product performance is stable.
In a second aspect of the invention, there is provided gradient heated pleated MXene/TiO 2/paraffin prepared by the method described above.
In a third aspect, the invention provides the application of the gradient heated pleated MXene/TiO 2/paraffin electromagnetic shielding material in the preparation of aerospace equipment, weaponry and civil infrastructures.
The invention has the beneficial effects that:
(1) The invention provides a method for gradient heating of the wrinkle MXene/TiO 2/paraffin with simple process, low cost and time saving and excellent electromagnetic shielding performance. The method can overcome the defects of the prior art, and solves the problems that the preparation process is complex, the cost is high, and the sample cannot be produced on a large scale in the prior art. The product can obviously improve the electromagnetic shielding performance of the MXene material.
(2) The invention adopts urea modified MXene with the fold morphology, and is partially oxidized into TiO 2 to prepare the fold MXene/TiO 2 after gradient heating, and finally the fold MXene/TiO 2/paraffin is prepared by mixing with paraffin, so that the urea modified MXene/TiO 2/paraffin has a large number of interfaces, and the result shows that: the method is an effective method for improving the electromagnetic shielding performance of the MXene material. The method mainly comprises the steps of enabling two-dimensional MXene nano sheets to be electrostatically self-assembled into a three-dimensional fold material under the action of urea, then conducting low-temperature air heating to enable MXene to be partially oxidized into TiO 2, finally conducting high-temperature heating under the protection of argon to enable urea on the surface of MXene to sublimate, retaining the fold morphology of the urea, and preparing gradient heated folds MXene/TiO 2 to be mixed with paraffin to serve as an electromagnetic shielding material.
(3) The preparation method is simple, has strong practicability and is easy to popularize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application.
FIG. 1 is a scanning microscope image of gradient heated wrinkle MXene/TiO 2/paraffin secondary electrons obtained in example 1 of the present invention.
FIG. 2 is a secondary electron scanning microscope image of gradient heated wrinkles MXene/TiO 2/paraffin wax obtained in example 2 of the present invention.
FIG. 3 is a secondary electron scanning microscope image of gradient heated wrinkle MXene/TiO 2/paraffin wax obtained in example 3 of the present invention.
FIG. 4 is a secondary electron scanning microscope image of gradient heated wrinkle MXene/TiO 2/paraffin wax obtained in example 4 of the present invention.
FIG. 5 is a secondary electron scanning microscope image of gradient heated wrinkle MXene/TiO 2/paraffin wax obtained in example 5 of the present invention.
FIG. 6 is a secondary electron scanning microscope image of gradient heated wrinkles MXene/TiO 2/paraffin wax obtained in example 6 of the present invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As described in the background art, when the MXene electromagnetic shielding material in the prior art is used, most of the MXene electromagnetic shielding material uses a complex process to enable the MXene to obtain a fold morphology, and the MXene electromagnetic shielding material is mechanically mixed with other substances to obtain better shielding performance, so that the structural stability and the electromagnetic shielding performance of the material are poor. The invention provides a method for mixing and stirring urea to enable MXene to have unique fold morphology, and then low-temperature air heating is used for controlling generation of TiO 2, high-temperature argon heating is used for removing urea and controlling generation of MXene defects. The simple urea mixing makes the operation of the MXene with the wrinkle appearance easy, and the gradient heating method for controlling the oxidation degree and defect degree of the MXene has simple process and can be used on a large scale. In addition, as the TiO 2 is obtained by oxidizing MXene, the structural stability of the two is better, and the preparation method of simple mixing and gradient heating is cheap and simple, and comprises the following steps:
step 1: performing magnetic stirring etching on 0.5g of precursor Ti 3AlC2 in a water solution of LiF and HCl at 35 ℃ in a polytetrafluoroethylene beaker for 24 hours, putting the solution into a 50ml centrifuge tube for centrifugation for multiple times until the pH of supernatant is more than 6, wherein the single centrifugation speed is 3500rpm, the centrifugation time is 10min, and obtaining the multi-layer MXene through precipitation;
step 2: putting the multi-layer MXene obtained in the step 1 into 100ml deionized water, performing ultrasonic treatment for 1h by using a 500W ultrasonic cleaner, centrifuging the solution for 1h, and freeze-drying the supernatant to obtain a two-dimensional few-layer MXene nano-sheet;
Step 3: dissolving the few-layer MXene nano-sheets obtained in the step 2 and urea into 100mL of deionized water, wherein the mass ratio of the two is 1:5, magnetically stirring for 1h, centrifuging to obtain precipitate, and freeze-drying to obtain the folded MXene/urea;
Step 4: and (3) placing the folded MXene/urea treated in the step (3) into a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, and keeping for 10-30min to obtain the folded MXene/TiO 2/urea.
Step 5: and (3) continuously heating the folded MXene/TiO 2/urea treated in the step (4), and continuously heating to 500-700 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, and keeping for 2 hours. Cooled to room temperature and the sample was removed from the pleat MXene/TiO 2.
Step 6: the wrinkling MXene/TiO 2 and paraffin are mixed according to the proportion of 1:9 to prepare the electromagnetic shielding material wrinkling MXene/TiO 2/paraffin.
In some embodiments, the temperature maintaining time in the step 4 may be 10-30min, preferably 10min.
In some embodiments, the heating temperature in step5 may be 500-700 ℃, preferably 600 ℃.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the following description will be made with reference to specific embodiments.
Example 1
Step 1: performing magnetic stirring etching on 0.5g of precursor Ti 3AlC2 in an aqueous solution of 0.5g of LiF and 10mL of 9mol/L HCl at 35 ℃ for 24h in a polytetrafluoroethylene beaker, putting into a 50ml centrifuge tube, centrifuging for multiple times until the pH value of the supernatant is more than 6, wherein the single centrifugation speed is 3500rpm, the centrifugation time is 10min, and obtaining the multi-layer MXene through precipitation;
Step 2: putting the multi-layer MXene obtained in the step 1 into 100ml deionized water, performing ultrasonic treatment for 1h by using a 500W ultrasonic cleaner, centrifuging the solution for 1h, and performing freeze drying treatment on the supernatant to obtain a two-dimensional few-layer MXene nano-sheet;
Step 3: dissolving the few-layer MXene nano-sheets obtained in the step 2 and urea into 100mL of deionized water, wherein the mass ratio of the two is 1:5, magnetically stirring for 1h, centrifuging to obtain precipitate, and freeze-drying to obtain the folded MXene/urea;
Step 4: and (3) placing the folded MXene/urea treated in the step (3) into a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, and keeping for 10min to obtain the folded MXene/TiO 2/urea.
Step 5: and (3) continuously heating the MXene/TiO 2/urea treated in the step (4), heating to 500 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, and keeping for 2 hours. Cooled to room temperature and the sample was removed from the pleat MXene/TiO 2.
Step 6: mixing the folded MXene/TiO 2 processed in the step 5 with paraffin melted at 80 ℃ in a ratio of 1:9, stirring with a spoon to uniformly mix, then placing into a forming machine to form a concentric circular ring block material with an outer diameter of 7mm and an inner diameter of 3.04mm, cutting the block material into 2mm by using a wallpaper knife, and finally preparing the folded MXene/TiO 2/paraffin electromagnetic shielding material.
For measurements, the electromagnetic shielding effectiveness EMI SE T of the corrugated MXene/TiO 2/paraffin electromagnetic shielding material was characterized by a vector network analyzer (Agilent Technologies, N5244A) in the range of 8.0-12.4 GHz.
Example 2
Step 1: performing magnetic stirring etching on 0.5g of precursor Ti 3AlC2 in an aqueous solution of 0.5g of LiF and 10mL of 9mol/L HCl at 35 ℃ for 24h in a polytetrafluoroethylene beaker, putting into a 50ml centrifuge tube, centrifuging for multiple times until the pH value of the supernatant is more than 6, wherein the single centrifugation speed is 3500rpm, the centrifugation time is 10min, and obtaining the multi-layer MXene through precipitation;
Step 2: putting the multi-layer MXene obtained in the step 1 into 100ml deionized water, performing ultrasonic treatment for 1h by using a 500W ultrasonic cleaner, centrifuging the solution for 1h, and performing freeze drying treatment on the supernatant to obtain a two-dimensional few-layer MXene nano-sheet;
Step 3: dissolving the few-layer MXene nano-sheets obtained in the step 2 and urea into 100mL of deionized water, wherein the mass ratio of the two is 1:5, magnetically stirring for 1h, centrifuging to obtain precipitate, and freeze-drying to obtain the folded MXene/urea;
Step 4: and (3) placing the folded MXene/urea treated in the step (3) into a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, and keeping for 10min to obtain the folded MXene/TiO 2/urea.
Step 5: and (3) continuously heating the MXene/TiO 2/urea treated in the step (4), heating to 600 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, and keeping for 2 hours. Cooled to room temperature and the sample was removed from the pleat MXene/TiO 2.
Step 6: mixing the folded MXene/TiO 2 processed in the step 5 with paraffin melted at 80 ℃ in a ratio of 1:9, stirring with a spoon to uniformly mix, then placing into a forming machine to form a concentric circular ring block material with an outer diameter of 7mm and an inner diameter of 3.04mm, cutting the block material into 2mm by using a wallpaper knife, and finally preparing the folded MXene/TiO 2/paraffin electromagnetic shielding material.
For measurements, the electromagnetic shielding effectiveness EMI SE T of the corrugated MXene/TiO 2/paraffin electromagnetic shielding material was characterized by a vector network analyzer (Agilent Technologies, N5244A) in the range of 8.0-12.4 GHz.
Example 3
Step 1: performing magnetic stirring etching on 0.5g of precursor Ti 3AlC2 in an aqueous solution of 0.5g of LiF and 10mL of 9mol/L HCl at 35 ℃ for 24h in a polytetrafluoroethylene beaker, putting into a 50ml centrifuge tube, centrifuging for multiple times until the pH value of the supernatant is more than 6, wherein the single centrifugation speed is 3500rpm, the centrifugation time is 10min, and obtaining the multi-layer MXene through precipitation;
Step 2: putting the multi-layer MXene obtained in the step 1 into 100ml deionized water, performing ultrasonic treatment for 1h by using a 500W ultrasonic cleaner, centrifuging the solution for 1h, and performing freeze drying treatment on the supernatant to obtain a two-dimensional few-layer MXene nano-sheet;
Step 3: dissolving the few-layer MXene nano-sheets obtained in the step 2 and urea into 100mL of deionized water, wherein the mass ratio of the two is 1:5, magnetically stirring for 1h, centrifuging to obtain precipitate, and freeze-drying to obtain the folded MXene/urea;
Step 4: and (3) placing the folded MXene/urea treated in the step (3) into a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, and keeping for 10min to obtain the folded MXene/TiO 2/urea.
Step 5: and (3) continuously heating the MXene/TiO 2/urea treated in the step (4), heating to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, and keeping for 2 hours. Cooled to room temperature and the sample was removed from the pleat MXene/TiO 2.
Step 6: mixing the folded MXene/TiO 2 processed in the step 5 with paraffin melted at 80 ℃ in a ratio of 1:9, stirring with a spoon to uniformly mix, then placing into a forming machine to form a concentric circular ring block material with an outer diameter of 7mm and an inner diameter of 3.04mm, cutting the block material into 2mm by using a wallpaper knife, and finally preparing the folded MXene/TiO 2/paraffin electromagnetic shielding material.
For measurements, the electromagnetic shielding effectiveness EMI SE T of the corrugated MXene/TiO 2/paraffin electromagnetic shielding material was characterized by a vector network analyzer (Agilent Technologies, N5244A) in the range of 8.0-12.4 GHz.
Example 4
Step 1: performing magnetic stirring etching on 0.5g of precursor Ti 3AlC2 in an aqueous solution of 0.5g of LiF and 10mL of 9mol/L HCl at 35 ℃ for 24h in a polytetrafluoroethylene beaker, putting into a 50ml centrifuge tube, centrifuging for multiple times until the pH value of the supernatant is more than 6, wherein the single centrifugation speed is 3500rpm, the centrifugation time is 10min, and obtaining the multi-layer MXene through precipitation;
Step 2: putting the multi-layer MXene obtained in the step 1 into 100ml deionized water, performing ultrasonic treatment for 1h by using a 500W ultrasonic cleaner, centrifuging the solution for 1h, and performing freeze drying treatment on the supernatant to obtain a two-dimensional few-layer MXene nano-sheet;
Step 3: dissolving the few-layer MXene nano-sheets obtained in the step 2 and urea into 100mL of deionized water, wherein the mass ratio of the two is 1:5, magnetically stirring for 1h, centrifuging to obtain precipitate, and freeze-drying to obtain the folded MXene/urea;
Step 4: and (3) placing the folded MXene/urea treated in the step (3) into a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, and keeping for 30min to obtain the folded MXene/TiO 2/urea.
Step 5: and (3) continuously heating the MXene/TiO 2/urea treated in the step (4), heating to 500 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, and keeping for 2 hours. Cooled to room temperature and the sample was removed from the pleat MXene/TiO 2.
Step 6: mixing the folded MXene/TiO 2 processed in the step 5 with paraffin melted at 80 ℃ in a ratio of 1:9, stirring with a spoon to uniformly mix, then placing into a forming machine to form a concentric circular ring block material with an outer diameter of 7mm and an inner diameter of 3.04mm, cutting the block material into 2mm by using a wallpaper knife, and finally preparing the folded MXene/TiO 2/paraffin electromagnetic shielding material.
For measurements, the electromagnetic shielding effectiveness EMI SE T of the corrugated MXene/TiO 2/paraffin electromagnetic shielding material was characterized by a vector network analyzer (Agilent Technologies, N5244A) in the range of 8.0-12.4 GHz.
Example 5
Step 1: performing magnetic stirring etching on 0.5g of precursor Ti 3AlC2 in an aqueous solution of 0.5g of LiF and 10mL of 9mol/L HCl at 35 ℃ for 24h in a polytetrafluoroethylene beaker, putting into a 50ml centrifuge tube, centrifuging for multiple times until the pH value of the supernatant is more than 6, wherein the single centrifugation speed is 3500rpm, the centrifugation time is 10min, and obtaining the multi-layer MXene through precipitation;
Step 2: putting the multi-layer MXene obtained in the step 1 into 100ml deionized water, performing ultrasonic treatment for 1h by using a 500W ultrasonic cleaner, centrifuging the solution for 1h, and performing freeze drying treatment on the supernatant to obtain a two-dimensional few-layer MXene nano-sheet;
Step 3: dissolving the few-layer MXene nano-sheets obtained in the step 2 and urea into 100mL of deionized water, wherein the mass ratio of the two is 1:5, magnetically stirring for 1h, centrifuging to obtain precipitate, and freeze-drying to obtain the folded MXene/urea;
Step 4: and (3) placing the folded MXene/urea treated in the step (3) into a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, and keeping for 30min to obtain the folded MXene/TiO 2/urea.
Step 5: and (3) continuously heating the MXene/TiO 2/urea treated in the step (4), heating to 600 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, and keeping for 2 hours. Cooled to room temperature and the sample was removed from the pleat MXene/TiO 2.
Step 6: mixing the folded MXene/TiO 2 processed in the step 5 with paraffin melted at 80 ℃ in a ratio of 1:9, stirring with a spoon to uniformly mix, then placing into a forming machine to form a concentric circular ring block material with an outer diameter of 7mm and an inner diameter of 3.04mm, cutting the block material into 2mm by using a wallpaper knife, and finally preparing the folded MXene/TiO 2/paraffin electromagnetic shielding material.
For measurements, the electromagnetic shielding effectiveness EMI SE T of the corrugated MXene/TiO 2/paraffin electromagnetic shielding material was characterized by a vector network analyzer (Agilent Technologies, N5244A) in the range of 8.0-12.4 GHz.
Example 6
Step 1: performing magnetic stirring etching on 0.5g of precursor Ti 3AlC2 in an aqueous solution of 0.5g of LiF and 10mL of 9mol/L HCl at 35 ℃ for 24h in a polytetrafluoroethylene beaker, putting into a 50ml centrifuge tube, centrifuging for multiple times until the pH value of the supernatant is more than 6, wherein the single centrifugation speed is 3500rpm, the centrifugation time is 10min, and obtaining the multi-layer MXene through precipitation;
Step 2: putting the multi-layer MXene obtained in the step 1 into 100ml deionized water, performing ultrasonic treatment for 1h by using a 500W ultrasonic cleaner, centrifuging the solution for 1h, and performing freeze drying treatment on the supernatant to obtain a two-dimensional few-layer MXene nano-sheet;
Step 3: dissolving the few-layer MXene nano-sheets obtained in the step 2 and urea into 100mL of deionized water, wherein the mass ratio of the two is 1:5, magnetically stirring for 1h, centrifuging to obtain precipitate, and freeze-drying to obtain the folded MXene/urea;
Step 4: and (3) placing the folded MXene/urea treated in the step (3) into a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under the atmosphere of air, and keeping for 30min to obtain the folded MXene/TiO 2/urea.
Step 5: and (3) continuously heating the MXene/TiO 2/urea treated in the step (4), heating to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, and keeping for 2 hours. Cooled to room temperature and the sample was removed from the pleat MXene/TiO 2.
Step 6: mixing the folded MXene/TiO 2 processed in the step 5 with paraffin melted at 80 ℃ in a ratio of 1:9, stirring with a spoon to uniformly mix, then placing into a forming machine to form a concentric circular ring block material with an outer diameter of 7mm and an inner diameter of 3.04mm, cutting the block material into 2mm by using a wallpaper knife, and finally preparing the folded MXene/TiO 2/paraffin electromagnetic shielding material.
For measurements, the electromagnetic shielding effectiveness EMI SE T of the corrugated MXene/TiO 2/paraffin electromagnetic shielding material was characterized by a vector network analyzer (Agilent Technologies, N5244A) in the range of 8.0-12.4 GHz.
Table 1 is an electromagnetic shielding effectiveness graph of examples 1-6MXene/TiO 2/paraffin electromagnetic shielding material, showing the corresponding maximum, minimum, and average values of EMI SE T. From the table, the electromagnetic shielding effectiveness of the MXene/TiO 2/paraffin wax of 6 examples is greater than 20dB in the range of 8.0-12.4GHz, which indicates potential application value. In the embodiment 2, the values of the EMI SE T are all larger than those corresponding to other embodiments, which shows that after the electromagnetic shielding material is oxidized for 10min at the low temperature of 200 ℃, the MXene/TiO 2/paraffin electromagnetic shielding material is prepared at the high temperature of 600 ℃ under the protection of argon, on one hand, the proper TiO 2 content generates more interfaces, on the other hand, certain conductivity is reserved, so that when the electromagnetic wave is incident on the surface of the material, one part of the electromagnetic wave is reflected back into the air, and the other part of the electromagnetic wave is fully absorbed into the material, and finally, the electromagnetic shielding performance is optimal.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention. While the foregoing description of the embodiments of the present invention has been presented in conjunction with the drawings, it should be understood that it is not intended to limit the scope of the invention, but rather, it is intended to cover all modifications or variations within the scope of the invention as defined by the claims of the present invention.
Claims (5)
1. A method for preparing gradient heated pleated Mxene/TiO 2/paraffin, comprising:
Uniformly mixing the two-dimensional few-layer Mxene nano-sheet and urea in a solvent to obtain an Mxene/urea material with a wrinkle morphology;
Heating the Mxene/urea material with the wrinkle morphology below 200 ℃ to obtain a wrinkle Mxene/TiO 2/urea compound;
heating the compound of the fold Mxene/TiO 2/urea in inert gas at 500-700 ℃ to obtain a gradient heated fold Mxene/TiO 2;
compounding the gradient heated fold Mxene/TiO 2 with paraffin to obtain the product;
Heating at 200 deg.c for 5-15 min or 25-35 min;
The mass ratio of the few-layer Mxene nano-sheets to urea is 1:5-8;
The mixing ratio of the wrinkling Mxene/TiO 2 and the paraffin is 1:9-12;
The preparation method of the two-dimensional few-layer Mxene nano-sheet comprises the following steps: carrying out ultrasonic and centrifugal treatment on the multilayer Mxene nano-sheet, and preparing a few-layer Mxene nano-sheet after freeze drying;
The preparation method of the multilayer Mxene nanosheets comprises the following steps: etching the precursor Ti 3AlC2 in the aqueous solution of LiF and HCl, and centrifuging to pH >6 to obtain the multilayer Mxene nano-sheet.
2. The method of preparing gradient heated pleated Mxene/TiO 2/paraffin according to claim 1, characterized in that the heating time below 200 ℃ is 10min or 30min.
3. The method of preparing a gradient heated pleated Mxene/TiO 2/paraffin according to claim 1, wherein the pleated Mxene/TiO 2/urea composite is heated at 600 ℃.
4. A gradient heated pleated Mxene/TiO 2/paraffin prepared by the method of any of claims 1-3.
5. The gradient heated pleated Mxene/TiO 2/paraffin of claim 4, wherein the gradient heated pleated Mxene/TiO 2/paraffin is used to make an electromagnetic shielding material.
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