CN116715926A - Preparation method of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material and corresponding material - Google Patents
Preparation method of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material and corresponding material Download PDFInfo
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- CN116715926A CN116715926A CN202310685075.7A CN202310685075A CN116715926A CN 116715926 A CN116715926 A CN 116715926A CN 202310685075 A CN202310685075 A CN 202310685075A CN 116715926 A CN116715926 A CN 116715926A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 141
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 94
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 94
- 239000011358 absorbing material Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title abstract description 24
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 84
- 239000000243 solution Substances 0.000 claims abstract description 66
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 42
- 239000001530 fumaric acid Substances 0.000 claims abstract description 42
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 39
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 37
- 239000013384 organic framework Substances 0.000 claims abstract description 34
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 30
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000010000 carbonizing Methods 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 88
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000001723 curing Methods 0.000 claims description 22
- 238000003760 magnetic stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 claims 3
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C09K3/00—Materials not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of wave-absorbing materials, in particular to a preparation method of a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material and a corresponding material, wherein the method comprises the following steps: preparing a mixed solution by preparing ferric chloride hexahydrate solution and fumaric acid solution, carrying out hydrothermal reaction on the mixed solution, respectively adopting absolute ethyl alcohol and distilled water to wash and dry the product of the hydrothermal reaction, and carbonizing the prepared iron-based organic framework precursor in an inert gas environment to prepare a derivative iron/carbon material; preparing polyvinylidene fluoride solution, dissolving derivative iron/carbon material into the polyvinylidene fluoride solution through fourth ultrasonic treatment, curing and heat-treating the prepared high polymer composite solution, and performing hot press forming treatment on the prepared solid film to obtain the polyvinylidene fluoride iron/carbon composite wave-absorbing material. The invention can improve the wave absorbing performance of the wave absorbing material, simplify the process and reduce the cost.
Description
Technical Field
The invention relates to the technical field, in particular to a preparation method of a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material and a corresponding material.
Background
Along with the rapid development of electronic information technology, electromagnetic waves play a role in communication equipment, medical equipment, industrial machines, 5G base stations and the like, bring convenience to people, and simultaneously bring a large amount of electromagnetic wave pollution, for example, electromagnetic interference can influence the normal operation of the electronic equipment, and electromagnetic radiation can cause harm to human health. Furthermore, in the military sector facing the complex electromagnetic environment in the battlefield, it is crucial that the weapon equipment has "stealth" properties.
The wave absorbing material can effectively consume the incident electromagnetic wave, thereby reducing or eliminating electromagnetic pollution. Whether or not the wave absorbing property of the wave absorbing material is excellent depends on two key factors: firstly, impedance matching, wherein the material is required to reduce reflection and transmission of incident electromagnetic waves as much as possible; and secondly, the attenuation characteristic is that the material can enhance the loss of electromagnetic waves through various loss mechanisms. The traditional wave-absorbing materials such as ferrite and metal micro powder are limited to be applied on a large scale due to the reasons of high density, single loss mechanism, narrow absorption frequency range and the like, and in order to prepare novel wave-absorbing materials with small density, thin thickness, wide effective absorption frequency range and high absorption strength, the absorption performance is enhanced in the field by adopting multi-component composite materials and doping modes.
The Chinese patent with publication number of CN 107541185A provides a zinc-doped ferrite/carbon nanotube wave-absorbing material and a preparation method thereof, wherein the method comprises the steps of acidizing carbon nanotubes in concentrated hydrochloric acid, carboxylating the carbon nanotubes with concentrated hydrogen peroxide, ball-milling and dispersing the carboxylated carbon nanotubes into an iron ion salt solution for oil bath stirring reaction, adding a dispersing agent and a precipitating agent into an iron salt solution, stirring, standing and curing, and washing and drying to obtain the ferrite/carbon nanotube wave-absorbing material. In the wave-absorbing material prepared by the method, the dispersibility of the carbon nano tube is improved, but the wave-absorbing performance of the material is only-14.1 dB, and the lower absorption strength of the wave-absorbing material does not accord with the development trend of 'thin, light, wide and strong' of the novel wave-absorbing material, and the large-scale industrial production of the wave-absorbing material is limited by the complexity of the material production process and the higher cost of raw materials.
Therefore, how to provide a method for preparing a wave-absorbing material, which can improve the wave-absorbing performance of the wave-absorbing material, simplify the process and reduce the cost, is a technical problem to be solved.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material and a corresponding material for overcoming the defects of the prior art.
In one aspect, the invention provides a preparation method of a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, which comprises the following steps:
step one, preparation of an iron-based organic framework precursor
Dissolving ferric chloride hexahydrate into N, N-dimethylformamide by first ultrasonic treatment according to a proportion to prepare ferric chloride hexahydrate solution;
dissolving fumaric acid into N, N-dimethylformamide by second ultrasonic treatment according to the proportion to prepare a fumaric acid solution;
dissolving fumaric acid solution into ferric chloride hexahydrate solution through third ultrasonic treatment according to the proportion to prepare a mixed solution;
carrying out hydrothermal reaction on the mixed solution, and respectively adopting absolute ethyl alcohol and distilled water to wash and dry the product of the hydrothermal reaction to prepare an iron-based organic framework precursor;
step two, carbonizing the precursor of the iron-based organic framework
Carbonizing an iron-based organic framework precursor in an inert gas environment to prepare a derivative iron/carbon material;
step three, preparation of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material
Preparing polyvinylidene fluoride, N-dimethylformamide and derived iron/carbon materials according to the proportion;
dissolving polyvinylidene fluoride into N, N-dimethylformamide through room temperature magnetic stirring treatment to prepare a polyvinylidene fluoride solution, dissolving derivative iron/carbon materials into the polyvinylidene fluoride solution through fourth ultrasonic treatment to prepare a high polymer composite solution, and carrying out curing heat treatment on the high polymer composite solution to prepare a solid film;
and carrying out hot press molding treatment on the prepared solid film to obtain the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material.
As a preferable mode of the invention, in the step one of the preparation method of the polyvinylidene fluoride-based iron/carbon composite wave absorbing material, the concentration of ferric chloride hexahydrate in the prepared ferric chloride hexahydrate solution is 0.05mol/L, the concentration of fumaric acid in the prepared fumaric acid solution is 0.05mol/L, and the ratio of the amounts of ferric chloride hexahydrate and fumaric acid substances in the prepared mixed solution is 1:1-1:3.
As a preferable mode of the invention, in the first step of the preparation method of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, the time of the first ultrasonic treatment, the second ultrasonic treatment and the third ultrasonic treatment is 15-30min.
As the preferable mode of the invention, in the step one of the preparation method of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, the temperature of the hydrothermal reaction is 100-150 ℃, the time of the hydrothermal reaction is 12-24 hours, the temperature of the drying treatment is 60 ℃, and the time of the drying treatment is 12-24 hours.
As a preferred aspect of the present invention, in the second step of the preparation method of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material of the present invention, the carbonization treatment includes: heating to 700-900 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, cooling to 500 ℃ at 10 ℃/min, and naturally cooling to room temperature.
In the third step of the preparation method of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, polyvinylidene fluoride, N-dimethylformamide and derived iron/carbon materials are prepared according to the proportion, and the preparation method comprises the following steps: n, N-dimethylformamide is provided with 4-6mg of polyvinylidene fluoride and 1-2mg of derivatized iron/carbon material per ml.
As the preferable mode of the invention, in the step three of the preparation method of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, the stirring speed of room temperature magnetic stirring treatment is 600r/min, the time of room temperature magnetic stirring is 30min, and the time of fourth ultrasonic treatment is 60min.
In the third step of the preparation method of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, the temperature of the curing heat treatment is 50 ℃, and the time of the curing heat treatment is 12 hours.
As the preferable mode of the invention, in the step three of the preparation method of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, the temperature of the hot-press molding treatment is 180-210 ℃, the pressure of the hot-press molding treatment is 3-4Mpa, and the time of the hot-press molding treatment is 10-15min.
In another aspect, the invention provides a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, which is prepared according to the method.
The preparation method of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material and the corresponding material have the following beneficial effects:
1. the method prepares the iron-based organic framework precursor under the solvothermal condition, and the morphology and the size of the product are uniform and controllable; and simultaneously, fumaric acid is used as a carbon source, so that the introduction of hetero atoms caused by adding additional carbon sources is avoided, and the method is simple and quick.
2. The invention utilizes the micromolecular gas matters escaping from the fumaric acid in the high-temperature carbonization process to lead the derivative iron/carbon material to have the characteristic of being porous, the porous structure is beneficial to the repeated reflection loss of electromagnetic waves in the material, the wave absorbing performance is effectively enhanced, and the density of the wave absorbing material is also lightened.
3. The polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared by the invention has high magnetic conductivity and strong magnetic loss performance, and the conductivity loss performance of carbon can be regulated and controlled by changing carbonization conditions, so that more electromagnetic waves are incident and are lost, the performance of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material is effectively improved, the wave-absorbing strength reaches-63.5 dB at 13.5GHz and the corresponding thickness is 1.5mm, the effective wave-absorbing frequency width is 4.4GHz (13.6-18 GHz), and the problems of low absorption strength and narrow effective wave-absorbing frequency band of the traditional wave-absorbing material are solved.
4. The preparation method is simple and high in yield, the raw materials are rich, cheap and easy to obtain, the industrial production is facilitated, and the prepared polyvinylidene fluoride-based iron/carbon composite wave-absorbing material is suitable for popularization and application in the fields of connectors, automatic driving, electronic communication, radio frequency identification, electronic devices, microwave darkrooms and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM morphology of the iron-based organic framework precursor material prepared in example 1 of the present invention.
Fig. 2 is an SEM morphology of the iron-based organic framework precursor material prepared in example 2 of the present invention.
Fig. 3 is an SEM morphology of the iron-based organic framework precursor material prepared in example 3 of the present invention.
Fig. 4 is an SEM morphology of the derivatized iron/carbon material prepared in example 3 of the invention.
Fig. 5 is an SEM morphology of the derivatized iron/carbon material prepared in example 4 of the invention.
FIG. 6 is an SEM topography of the derivatized iron/carbon material of example 5 of the invention.
Fig. 7 is a laser raman spectrum of the derivatized iron/carbon material prepared in example 3 of the invention.
Fig. 8 is a laser raman spectrum of the derivatized iron/carbon material prepared in example 4 of the invention.
Fig. 9 is a laser raman spectrum of the derivatized iron/carbon material prepared in example 5 of the invention.
FIG. 10 is a graph showing the reflection loss of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared in example 3 of the present invention at a thickness of 1.5 mm.
FIG. 11 is a graph showing the reflection loss of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared in example 4 of the present invention at a thickness of 1.4 mm.
FIG. 12 is a graph showing the reflection loss of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared in example 5 of the present invention at a thickness of 1.7 mm.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
It should be noted that, without conflict, the following embodiments and features in the embodiments may be combined with each other; and, based on the embodiments in this disclosure, all other embodiments that may be made by one of ordinary skill in the art without inventive effort are within the scope of the present disclosure.
It is noted that various aspects of the embodiments are described below within the scope of the following claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present disclosure, one skilled in the art will appreciate that one aspect described herein may be implemented independently of any other aspect, and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number of the aspects set forth herein. In addition, such apparatus may be implemented and/or such methods practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
The technical principle of the invention is as follows:
the method prepares the iron-based organic framework precursor under the solvothermal condition, and the morphology and the size of the product are uniform and controllable; and simultaneously, fumaric acid is used as a carbon source, so that the introduction of hetero atoms caused by adding additional carbon sources is avoided, and the method is simple and quick.
The invention utilizes the micromolecular gas matters escaping from the fumaric acid in the high-temperature carbonization process to lead the derivative iron/carbon material to have the characteristic of being porous, the porous structure is beneficial to the repeated reflection loss of electromagnetic waves in the material, the wave absorbing performance is effectively enhanced, and the density of the wave absorbing material is also lightened.
The polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared by the invention has high magnetic conductivity and strong magnetic loss performance, and the conductivity loss performance of carbon can be regulated and controlled by changing carbonization conditions, so that more electromagnetic waves are incident and are lost, the performance of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material is effectively improved, the wave-absorbing strength reaches-63.5 dB at 13.5GHz and the corresponding thickness is 1.5mm, the effective wave-absorbing frequency width is 4.4GHz (13.6-18 GHz), and the problems of low absorption strength and narrow effective wave-absorbing frequency band of the traditional wave-absorbing material are solved.
The preparation method is simple and high in yield, the raw materials are rich, cheap and easy to obtain, the industrial production is facilitated, and the prepared polyvinylidene fluoride-based iron/carbon composite wave-absorbing material is suitable for popularization and application in the fields of connectors, automatic driving, electronic communication, radio frequency identification, electronic devices, microwave darkrooms and the like.
Example 1
Step one, preparation of an iron-based organic framework precursor
Dissolving ferric chloride hexahydrate into N, N-dimethylformamide by first ultrasonic treatment for 15min according to the proportion to prepare a ferric chloride hexahydrate solution with the concentration of 0.05 mol/L;
dissolving fumaric acid into N, N-dimethylformamide by a second ultrasonic treatment for 15min according to the proportion to prepare a fumaric acid solution with the concentration of fumaric acid of 0.05 mol/L;
dissolving fumaric acid solution into ferric chloride hexahydrate solution through third ultrasonic treatment for 15min according to the proportion to prepare mixed solution with the mass ratio of ferric chloride hexahydrate to fumaric acid being 1:3;
carrying out hydrothermal reaction on the mixed solution, wherein the temperature of the hydrothermal reaction is 100 ℃, the time of the hydrothermal reaction is 12 hours, washing and drying the product of the hydrothermal reaction by adopting absolute ethyl alcohol and distilled water respectively, and the drying temperature is 60 ℃ and the drying time is 15 hours, so as to prepare the iron-based organic skeleton precursor;
step two, carbonizing the precursor of the iron-based organic framework
Carbonizing an iron-based organic framework precursor in an inert gas environment, heating to 900 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, cooling to 500 ℃ at a temperature of 10 ℃/min, and naturally cooling to room temperature to prepare a derivative iron/carbon material;
step three, preparation of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material
Preparing 4-6mg of polyvinylidene fluoride and 1-2mg of derivative iron/carbon materials according to each milliliter of N, N-dimethylformamide;
dissolving 90mg of polyvinylidene fluoride into 15ml of N, N-dimethylformamide through room temperature magnetic stirring treatment, wherein the stirring speed of the room temperature magnetic stirring treatment is 600r/min, the room temperature magnetic stirring time is 30min, a polyvinylidene fluoride solution is prepared, dissolving 15mg of derivative iron/carbon material into the polyvinylidene fluoride solution through fourth ultrasonic treatment for 60min, a high polymer composite solution is prepared, and curing heat treatment is carried out on the high polymer composite solution, wherein the temperature of the curing heat treatment is 50 ℃, and the time of the curing heat treatment is 12h, so that a solid film is prepared;
and carrying out hot-press forming treatment on the prepared solid film, wherein the temperature of the hot-press forming treatment is 180 ℃, the pressure of the hot-press forming treatment is 3Mpa, and the time of the hot-press forming treatment is 10min, so as to obtain the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material.
Example 2
Step one, preparation of an iron-based organic framework precursor
Dissolving ferric chloride hexahydrate into N, N-dimethylformamide by first ultrasonic treatment for 20min according to the proportion to prepare a ferric chloride hexahydrate solution with the concentration of 0.05 mol/L;
dissolving fumaric acid into N, N-dimethylformamide by a second ultrasonic treatment for 20min according to the proportion to prepare a fumaric acid solution with the concentration of fumaric acid of 0.05 mol/L;
dissolving fumaric acid solution into ferric chloride hexahydrate solution through third ultrasonic treatment for 20min according to the proportion to prepare mixed solution with the mass ratio of ferric chloride hexahydrate to fumaric acid being 1:2;
carrying out hydrothermal reaction on the mixed solution, wherein the temperature of the hydrothermal reaction is 120 ℃, the time of the hydrothermal reaction is 15 hours, washing and drying the product of the hydrothermal reaction by adopting absolute ethyl alcohol and distilled water respectively, and the drying temperature is 60 ℃ and the drying time is 24 hours, so as to prepare the iron-based organic skeleton precursor;
step two, carbonizing the precursor of the iron-based organic framework
Carbonizing an iron-based organic framework precursor in an inert gas environment, heating to 900 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, cooling to 500 ℃ at a temperature of 10 ℃/min, and naturally cooling to room temperature to prepare a derivative iron/carbon material;
step three, preparation of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material
Preparing 4-6mg of polyvinylidene fluoride and 1-2mg of derivative iron/carbon materials according to each milliliter of N, N-dimethylformamide;
dissolving 60mg of polyvinylidene fluoride into 10ml of N, N-dimethylformamide through room temperature magnetic stirring treatment, wherein the stirring speed of the room temperature magnetic stirring treatment is 600r/min, the room temperature magnetic stirring time is 30min, a polyvinylidene fluoride solution is prepared, dissolving 20mg of derivative iron/carbon material into the polyvinylidene fluoride solution through fourth ultrasonic treatment for 60min, a high polymer composite solution is prepared, and carrying out curing heat treatment on the high polymer composite solution, wherein the temperature of the curing heat treatment is 50 ℃, and the curing heat treatment time is 12h, so that a solid film is prepared;
and carrying out hot-press forming treatment on the prepared solid film, wherein the temperature of the hot-press forming treatment is 200 ℃, the pressure of the hot-press forming treatment is 3Mpa, and the time of the hot-press forming treatment is 15min, so as to obtain the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material.
Example 3
Step one, preparation of an iron-based organic framework precursor
Dissolving ferric chloride hexahydrate into N, N-dimethylformamide by first ultrasonic treatment for 30min according to the proportion to prepare a ferric chloride hexahydrate solution with the concentration of 0.05 mol/L;
dissolving fumaric acid into N, N-dimethylformamide by second ultrasonic treatment for 30min according to the proportion to prepare a fumaric acid solution with the concentration of fumaric acid of 0.05 mol/L;
dissolving fumaric acid solution into ferric chloride hexahydrate solution through third ultrasonic treatment for 30min according to the proportion to prepare mixed solution with the mass ratio of ferric chloride hexahydrate to fumaric acid being 1:1;
carrying out hydrothermal reaction on the mixed solution, wherein the temperature of the hydrothermal reaction is 150 ℃, the time of the hydrothermal reaction is 24 hours, washing and drying the product of the hydrothermal reaction by adopting absolute ethyl alcohol and distilled water respectively, and the drying temperature is 60 ℃ and the drying time is 12 hours, so as to prepare the iron-based organic skeleton precursor;
step two, carbonizing the precursor of the iron-based organic framework
Carbonizing an iron-based organic framework precursor in an inert gas environment, heating to 900 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, cooling to 500 ℃ at a temperature of 10 ℃/min, and naturally cooling to room temperature to prepare a derivative iron/carbon material;
step three, preparation of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material
Preparing 4-6mg of polyvinylidene fluoride and 1-2mg of derivative iron/carbon materials according to each milliliter of N, N-dimethylformamide;
dissolving 80mg of polyvinylidene fluoride into 20ml of N, N-dimethylformamide through room temperature magnetic stirring treatment, wherein the stirring speed of the room temperature magnetic stirring treatment is 600r/min, the room temperature magnetic stirring time is 30min, a polyvinylidene fluoride solution is prepared, dissolving 20mg of derivative iron/carbon material into the polyvinylidene fluoride solution through fourth ultrasonic treatment for 60min, a high polymer composite solution is prepared, and carrying out curing heat treatment on the high polymer composite solution, wherein the temperature of the curing heat treatment is 50 ℃, and the curing heat treatment time is 12h, so that a solid film is prepared;
and carrying out hot-press forming treatment on the prepared solid film, wherein the temperature of the hot-press forming treatment is 210 ℃, the pressure of the hot-press forming treatment is 4Mpa, and the time of the hot-press forming treatment is 15min, so as to obtain the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material.
Example 4
Step one, preparation of an iron-based organic framework precursor
Dissolving ferric chloride hexahydrate into N, N-dimethylformamide by first ultrasonic treatment for 30min according to the proportion to prepare a ferric chloride hexahydrate solution with the concentration of 0.05 mol/L;
dissolving fumaric acid into N, N-dimethylformamide by second ultrasonic treatment for 30min according to the proportion to prepare a fumaric acid solution with the concentration of fumaric acid of 0.05 mol/L;
dissolving fumaric acid solution into ferric chloride hexahydrate solution through third ultrasonic treatment for 30min according to the proportion to prepare mixed solution with the mass ratio of ferric chloride hexahydrate to fumaric acid being 1:1;
carrying out hydrothermal reaction on the mixed solution, wherein the temperature of the hydrothermal reaction is 150 ℃, the time of the hydrothermal reaction is 24 hours, washing and drying the product of the hydrothermal reaction by adopting absolute ethyl alcohol and distilled water respectively, and the drying temperature is 60 ℃ and the drying time is 12 hours, so as to prepare the iron-based organic skeleton precursor;
step two, carbonizing the precursor of the iron-based organic framework
Carbonizing an iron-based organic framework precursor in an inert gas environment, heating to 800 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, cooling to 500 ℃ at a temperature of 10 ℃/min, and naturally cooling to room temperature to prepare a derivative iron/carbon material;
step three, preparation of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material
Preparing 4-6mg of polyvinylidene fluoride and 1-2mg of derivative iron/carbon materials according to each milliliter of N, N-dimethylformamide;
dissolving 20mg of polyvinylidene fluoride into 5ml of N, N-dimethylformamide through room temperature magnetic stirring treatment, wherein the stirring speed of the room temperature magnetic stirring treatment is 600r/min, the room temperature magnetic stirring time is 30min, so as to prepare a polyvinylidene fluoride solution, dissolving 5mg of derivative iron/carbon material into the polyvinylidene fluoride solution through fourth ultrasonic treatment for 60min, so as to prepare a high polymer composite solution, and carrying out curing heat treatment on the high polymer composite solution, wherein the temperature of the curing heat treatment is 50 ℃, and the curing heat treatment time is 12h, so that a solid film is prepared;
and carrying out hot-press forming treatment on the prepared solid film, wherein the temperature of the hot-press forming treatment is 210 ℃, the pressure of the hot-press forming treatment is 4Mpa, and the time of the hot-press forming treatment is 15min, so as to obtain the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material.
Example 5
Step one, preparation of an iron-based organic framework precursor
Dissolving ferric chloride hexahydrate into N, N-dimethylformamide by first ultrasonic treatment for 30min according to the proportion to prepare a ferric chloride hexahydrate solution with the concentration of 0.05 mol/L;
dissolving fumaric acid into N, N-dimethylformamide by second ultrasonic treatment for 30min according to the proportion to prepare a fumaric acid solution with the concentration of fumaric acid of 0.05 mol/L;
dissolving fumaric acid solution into ferric chloride hexahydrate solution through third ultrasonic treatment for 30min according to the proportion to prepare mixed solution with the mass ratio of ferric chloride hexahydrate to fumaric acid being 1:1;
carrying out hydrothermal reaction on the mixed solution, wherein the temperature of the hydrothermal reaction is 150 ℃, the time of the hydrothermal reaction is 24 hours, washing and drying the product of the hydrothermal reaction by adopting absolute ethyl alcohol and distilled water respectively, and the drying temperature is 60 ℃ and the drying time is 12 hours, so as to prepare the iron-based organic skeleton precursor;
step two, carbonizing the precursor of the iron-based organic framework
Carbonizing an iron-based organic framework precursor in an inert gas environment, heating to 700 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, cooling to 500 ℃ at a temperature of 10 ℃/min, and naturally cooling to room temperature to prepare a derivative iron/carbon material;
step three, preparation of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material
Preparing 4-6mg of polyvinylidene fluoride and 1-2mg of derivative iron/carbon materials according to each milliliter of N, N-dimethylformamide;
dissolving 80mg of polyvinylidene fluoride into 20ml of N, N-dimethylformamide through room temperature magnetic stirring treatment, wherein the stirring speed of the room temperature magnetic stirring treatment is 600r/min, the room temperature magnetic stirring time is 30min, a polyvinylidene fluoride solution is prepared, dissolving 20mg of derivative iron/carbon material into the polyvinylidene fluoride solution through fourth ultrasonic treatment for 60min, a high polymer composite solution is prepared, and carrying out curing heat treatment on the high polymer composite solution, wherein the temperature of the curing heat treatment is 50 ℃, and the curing heat treatment time is 12h, so that a solid film is prepared;
and carrying out hot-press forming treatment on the prepared solid film, wherein the temperature of the hot-press forming treatment is 210 ℃, the pressure of the hot-press forming treatment is 4Mpa, and the time of the hot-press forming treatment is 15min, so as to obtain the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material.
Example 6
The apparent morphology of the iron-based organic framework precursor materials prepared in example 1, example 2 and example 3 was observed by using a cold field emission scanning electron microscope of the model Hitachi S4800, and the acceleration voltage used was 5kV or 10kV, and SEM morphology diagrams of the iron-based organic framework precursor materials prepared in example 1, example 2 and example 3 were sequentially shown in fig. 1, fig. 2 and fig. 3.
As shown in fig. 1, 2 and 3, SEM morphology of the iron-based organic framework precursors prepared in examples 1 to 3 is uniform, and as the reaction temperature and reaction time are increased, the degree of uniformity of the structure is continuously improved, the transition from the sheet shape to the spindle shape is made, the length of the spindle-shaped iron-based organic framework precursor is about 2.1 μm, the diameter is about 0.81 μm, and the surface smoothness is also continuously improved.
The apparent morphologies of the derived iron/carbon materials prepared in example 3, example 4 and example 5 were observed using a cold field emission scanning electron microscope model Hitachi S4800, using an acceleration voltage of 5kV or 10kV, and SEM morphologies of the derived iron/carbon materials prepared in example 3, example 4 and example 5 are shown in fig. 4, 5 and 6.
As shown in fig. 4, 5 and 6, after the iron-based organic framework precursor materials prepared in example 3, example 4 and example 5 were subjected to higher carbonization temperatures to obtain derivative iron/carbon materials, spindle-like structure was still maintained, and as the carbonization temperature was increased from 700 ℃ to 900 ℃, the surface smoothness was continuously improved, and reduced iron particles were gradually developed from the surface of the material matrix to the inside of the embedded material during carbonization.
The graphitization degree of the derived iron/carbon materials prepared in example 3, example 4 and example 5 was tested by using a laser raman spectrometer (invita qntor) using an excitation wavelength of 532nm and a spectral range of 600-2200cm -1 Laser raman spectra of the derived iron/carbon materials prepared in example 3, example 4 and example 5 are shown in fig. 7, fig. 8 and fig. 9 in sequence.
In the laser Raman spectrum, at 1341cm -1 Id peak at 1586cm -1 The ratio of Ig peaks (Id/Ig) at the sites represents the graphitization degree of the material, and the smaller the ratio is, the higher the graphitization degree of the material is. As shown in fig. 7, 8 and 9, the Id/Ig values of the derivative iron/carbon materials prepared in example 3, example 4 and example 5 were 0.74, 0.80 and 0.89 in order, because the higher the carbonization temperature, the more energy was absorbed by the carbon, the higher the graphitization degree of the material, and correspondingly, the better the conductivity of the material.
The dielectric magnetic parameters of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing materials prepared in example 3, example 4 and example 5 are respectively detected in the frequency range of 2-18GHz by using a vector network analyzer with the model of N5230C PNA-L by using a coaxial cable method, so as to obtain a reflection loss curve graph 10-12.
Specifically, fig. 10 is a graph showing reflection loss at a thickness of 1.5mm of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared in example 3. As can be seen from FIG. 10, the optimum reflection loss of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared in example 3 was-63.5 dB, and the effective absorption bandwidth (RL. Ltoreq. -10 dB) was 4.4GHz, because the higher carbonization temperature provided the electric conduction loss and the magnetic loss to the partially graphitized carbon in the carbon component, so that the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material had the optimum wave-absorbing performance.
FIG. 11 is a graph showing the reflection loss of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared in example 4 at a thickness of 1.4 mm. As can be seen from fig. 11. The reflection loss of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material is-24.6 dB, and the effective absorption bandwidth (RL is less than or equal to-10 dB) is 3.8GHz, because lamellar protrusions on the surface of the derivative iron/carbon material in the tissue of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material can form multiple reflection loss on incident electromagnetic waves.
FIG. 12 is a graph showing the reflection loss of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material prepared in example 5 at a thickness of 1.7 mm. As can be seen from FIG. 12, the reflection loss of the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material is-53.1 dB, the effective absorption bandwidth (RL is less than or equal to-10 dB) is 4.4GHz, and the efficient absorption of electromagnetic waves can be effectively realized.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the present invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (10)
1. A method for preparing a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, which is characterized by comprising the following steps:
step one, preparation of an iron-based organic framework precursor
Dissolving ferric chloride hexahydrate into N, N-dimethylformamide by first ultrasonic treatment according to a proportion to prepare ferric chloride hexahydrate solution;
dissolving fumaric acid into N, N-dimethylformamide by second ultrasonic treatment according to the proportion to prepare a fumaric acid solution;
dissolving fumaric acid solution into ferric chloride hexahydrate solution through third ultrasonic treatment according to the proportion to prepare a mixed solution;
carrying out hydrothermal reaction on the mixed solution, and respectively adopting absolute ethyl alcohol and distilled water to wash and dry the product of the hydrothermal reaction to prepare an iron-based organic framework precursor;
step two, carbonizing the precursor of the iron-based organic framework
Carbonizing an iron-based organic framework precursor in an inert gas environment to prepare a derivative iron/carbon material;
step three, preparation of polyvinylidene fluoride-based iron/carbon composite wave-absorbing material
Preparing polyvinylidene fluoride, N-dimethylformamide and derived iron/carbon materials according to the proportion;
dissolving polyvinylidene fluoride into N, N-dimethylformamide through room temperature magnetic stirring treatment to prepare a polyvinylidene fluoride solution, dissolving derivative iron/carbon materials into the polyvinylidene fluoride solution through fourth ultrasonic treatment to prepare a high polymer composite solution, and carrying out curing heat treatment on the high polymer composite solution to prepare a solid film;
and carrying out hot press molding treatment on the prepared solid film to obtain the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material.
2. The method for producing a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material according to claim 1, wherein in the first step, the concentration of iron chloride hexahydrate in the produced iron chloride hexahydrate solution is 0.05mol/L, the concentration of fumaric acid in the produced fumaric acid solution is 0.05mol/L, and the ratio of the amounts of the iron chloride hexahydrate to the fumaric acid in the produced mixed solution is 1:1 to 1:3.
3. The method for preparing a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material according to claim 1, wherein in the first step, the time of the first ultrasonic treatment, the second ultrasonic treatment and the third ultrasonic treatment is 15-30min.
4. The method for preparing a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material according to claim 1, wherein in the first step, the temperature of the hydrothermal reaction is 100-150 ℃, the time of the hydrothermal reaction is 12-24 hours, the temperature of the drying treatment is 60 ℃, and the time of the drying treatment is 12-24 hours.
5. The method for producing a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material according to claim 1, wherein in the second step, the carbonization treatment comprises: heating to 700-900 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, cooling to 500 ℃ at 10 ℃/min, and naturally cooling to room temperature.
6. The method for preparing the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material according to claim 1, wherein in the third step, polyvinylidene fluoride, N-dimethylformamide and derived iron/carbon materials are prepared according to a proportion, and the method comprises the following steps: n, N-dimethylformamide is provided with 4-6mg of polyvinylidene fluoride and 1-2mg of derivatized iron/carbon material per ml.
7. The method for preparing a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material according to claim 1, wherein in the third step, the stirring speed of the room temperature magnetic stirring treatment is 600r/min, the time of the room temperature magnetic stirring is 30min, and the time of the fourth ultrasonic treatment is 60min.
8. The method for preparing a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material according to claim 1, wherein in the third step, the temperature of the curing heat treatment is 50 ℃, and the time of the curing heat treatment is 12 hours.
9. The method for preparing a polyvinylidene fluoride-based iron/carbon composite wave-absorbing material according to claim 1, wherein in the third step, the temperature of the hot press forming treatment is 180-210 ℃, the pressure of the hot press forming treatment is 3-4Mpa, and the time of the hot press forming treatment is 10-15min.
10. A polyvinylidene fluoride-based iron/carbon composite wave-absorbing material, characterized in that the polyvinylidene fluoride-based iron/carbon composite wave-absorbing material is produced according to the method of any one of claims 1 to 9.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108154984A (en) * | 2017-12-26 | 2018-06-12 | 山东大学 | A kind of porous ferroferric oxide/carbon nano rod shape electromagnetic wave absorbent material and preparation method and application |
| CN111560149A (en) * | 2020-05-27 | 2020-08-21 | 嵊州市鉴亭新材料科技有限公司 | Carbon-coated Fe3O4-polyvinylidene fluoride magnetic dielectric material and preparation method thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108154984A (en) * | 2017-12-26 | 2018-06-12 | 山东大学 | A kind of porous ferroferric oxide/carbon nano rod shape electromagnetic wave absorbent material and preparation method and application |
| CN111560149A (en) * | 2020-05-27 | 2020-08-21 | 嵊州市鉴亭新材料科技有限公司 | Carbon-coated Fe3O4-polyvinylidene fluoride magnetic dielectric material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李潇: "金属有机骨架材料及衍生物的制备与吸波性能研究", 中国优秀硕士学位论文全文数据库 工程科技I辑, no. 1, 15 January 2022 (2022-01-15), pages 020 - 970 * |
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