CN108154984B - Porous ferroferric oxide/carbon nano rod-shaped electromagnetic wave absorption material and preparation method and application thereof - Google Patents
Porous ferroferric oxide/carbon nano rod-shaped electromagnetic wave absorption material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a porous ferroferric oxide/carbon nano rod-shaped electromagnetic wave absorption material and a preparation method and application thereof. The porous ferroferric oxide/carbon nanorod composite material is multiphase nano composite powder consisting of carbon and ferroferric oxide, and is a nanorod with a porous structure and the length of 1.0-1.2 mu m. The preparation method comprises the following steps: dissolving ferric chloride hexahydrate, fumaric acid and the like serving as raw materials in deionized water, reacting to obtain a precursor, and calcining in a nitrogen atmosphere to directly synthesize the porous ferroferric oxide/carbon nanorod composite material. The obtained porous ferroferric oxide/carbon nanorod composite material has the characteristics of good stability and uniformity, good electromagnetic wave absorption performance, wide absorption coverage frequency range, strong corrosion resistance and oxidation resistance and low cost, and is used for manufacturing electromagnetic absorbers.
Description
Technical Field
The invention relates to a porous ferroferric oxide/carbon nanorod electromagnetic wave absorbing material obtained from a metal framework derivative (MOF), and a preparation method and application thereof, and belongs to the technical field of electromagnetic wave absorbing materials.
Background
With the rapid development of radio communication technology in military and civil applications, increasing electromagnetic interference has caused electromagnetic wave absorbing materials to receive more and more attention. On the other hand, the electromagnetic wave absorbing material is used as an important component of the stealth technology, and can convert energy into heat energy to be absorbed through dielectric loss of incident electromagnetic waves on the premise that the appearance of the equipment is not changed, so that the detected rate is reduced, and the survival rate of the equipment is improved. Therefore, the research of the electromagnetic wave absorbing material technology and the application thereof in airplanes, ships, tanks and rocket projectiles are one of national defense high-tech technologies which are mainly developed in various countries in the world. Among a plurality of potential wave-absorbing materials, carbon materials are called as research hotspots due to the advantages of large specific surface area, abundant reserves, low preparation cost, low density and the like, and carbon nanotubes, graphene, carbon fibers and the like are reported in literatures. However, for a absorbing material, the absorption properties of a absorbing material are mainly determined by its dielectric constant and magnetic permeability. According to the impedance matching condition Zin＝Z0(μr/r)1/2While impedance matching is difficult to achieve only by means of single magnetic loss or dielectric loss, carbon materials as a non-magnetic material have poor impedance matching effect, and further development and application of the carbon materials are limited. In order to improve this, researchers combine carbon materials and magnetic materials by constructing composite materials, so as to improve the impedance matching level and further obtain significantly improved electromagnetic wave absorption performance. In addition, compared with magnetic metal materials such as iron, cobalt, nickel and the like, ferroferric oxide is a hot point of research in recent years because of better oxidation resistance and thermal stability and higher curie temperature. For example, document j.phys.chem.c, 2011, 115(14025) produces an Fe3O4the/C nano rod has the maximum absorption intensity of-27.9 dB at the thickness of 2 mm. Document ACS appl. Mater. interfaces 2014,6(12997) reports a core-shell structure Fe3O4the/C nanosphere has the reflection loss reaching 20.0dB at 13.4 GHz.
According to the reports in the literature, there are two general methods for preparing the ferroferric oxide particle modified carbon nano composite material. The first is to mix organic macromolecule and metal salt or oxide under protective atmosphere, under the action of high temperature, carbon decomposed from organic macromolecule is used as reducing agent to obtain metal oxide; the second method is to perform chemical reduction directly, in which expensive metal oxide is first compounded with carbon and then reduced directly, such as gamma-ray method; in addition, chemical vapor deposition, arc discharge, etc. are also available, but these methods have the disadvantages of complicated injection steps and complicated equipment. In recent years, means for preparing carbon-based composite materials by metal framework derivatives (MOFs) have received increasing attention from researchers. The MOF contains carbon and metal ions simultaneously, so that the MOF serves as a carbon source and also provides a metal raw material, and the polymerization and the reduction of the metal ions can be carried out simultaneously. On the other hand, the metal or oxide obtained by MOF often has a porous structure, which is more beneficial to electromagnetic wave absorption. The document ACS appl. mater. interfaces 2015,7(13604) reports a porous cobalt-carbon polyhedron derived from MOF with a maximum absorption intensity of-35.3 dB at a thickness of 4 mm. However, the oxidation resistance of the metallic cobalt is weak, which is not favorable for the stability of the wave-absorbing material. Therefore, the invention provides a ferroferric oxide/carbon material obtained from MOF and application thereof in the field of wave absorption.
Disclosure of Invention
Aiming at the defects of the existing ferroferric oxide electromagnetic wave absorbing material, the invention provides a porous ferroferric oxide/carbon nanorod composite electromagnetic wave absorbing material which has low cost, easy preparation and high electromagnetic wave absorption and a preparation method thereof.
The invention also provides application of the porous ferroferric oxide/carbon nanorod composite powder.
Summary of The Invention
The porous ferroferric oxide/carbon nanorod composite material is prepared by adopting a solvothermal and protective atmosphere calcining synthetic route, and has the characteristics of high saturation magnetic susceptibility, high coercive force, light weight, strong oxidation resistance, excellent electromagnetic wave absorption performance, simple preparation process, low cost and the like.
Detailed Description
The technical scheme of the invention is as follows:
a porous ferroferric oxide/carbon nanorod composite electromagnetic wave absorbing material is multiphase nano composite powder consisting of carbon and ferroferric oxide; wherein, ferroferric oxide particles are embedded in the carbon lamella to form the monodisperse nano rod with a porous structure.
According to the present invention, it is preferable that the size of the composite electromagnetic wave absorption material is 1.0 to 1.2 μm and the pore diameter is 1 to 20 nm. Pore structures exist among the ferroferric oxide particles and inside the nano carbon layer.
According to the invention, the size of the ferroferric oxide particles is preferably 40-50 nm.
According to the invention, preferably, in the porous ferroferric oxide/carbon nanorod composite material, the mass ratio of carbon to ferroferric oxide is (1-40) to (60-99).
According to the present invention, preferably, the carbon is amorphous carbon.
The electromagnetic wave absorption material of the porous ferroferric oxide/carbon nanorod composite material has the saturation magnetic susceptibility of 52.6emu/g and the coercive force HcjCan reach 100.8 Oe; when the content of the porous ferroferric oxide/carbon nanorod composite material in the prepared absorber is 40% by mass, the prepared absorber absorbs RL electromagnetic waves in the frequency range of 2-17.5GHz<10dB, i.e. 90% of the electromagnetic waves are absorbed.
According to the invention, the preparation method of the porous ferroferric oxide/carbon nanorod composite electromagnetic wave absorption material comprises the following steps:
(1) taking trivalent inorganic ferric salt and fumaric acid as raw materials of a synthetic ferroferric oxide precursor, and taking deionized water as a solvent; mixing the inorganic ferric salt and fumaric acid according to a molar ratio of 1:1, dissolving in deionized water, reacting for 2-30 hours at the temperature of 100-400 ℃ under a closed condition, and washing and drying a product after the reaction is finished to prepare a precursor;
(2) and (3) placing the precursor in a nitrogen atmosphere tube furnace, and preserving heat for 1-5 hours at 500-1000 ℃ to obtain the porous ferroferric oxide/carbon nanorod composite material.
According to the present invention, it is preferred that the reaction temperature in step (1) is 100-200 ℃ and the reaction time is 1-10 hours.
According to the present invention, it is preferable that the molar ratio of the inorganic iron salt to the fumaric acid in the step (1) is 1: 1;
preferably, the trivalent inorganic iron salt is ferric chloride hexahydrate (FeCl)3·6H2O)。
In the step (1) of the present invention, the amount of deionized water as a solvent is not particularly limited, and may be a conventional amount.
According to the present invention, it is preferred that the reaction temperature in step (2) is 500-900 ℃ and the reaction time is 1-5 hours.
The step (2) of the invention is to carry out reaction in a tubular furnace under nitrogen atmosphere to directly prepare the porous ferroferric oxide/carbon nano rod composite material.
The reaction principle of the invention is as follows:
under hydrothermal conditions, e.g. ferric chloride hexahydrate (FeCl)3·6H2Fe in O)3+And carrying out complexation reaction with ions generated by dissolving fumaric acid to generate precursor precipitate with a rod-shaped structure with the length of 1.0-1.2 mu m. And (3) performing subsequent calcination treatment in a nitrogen atmosphere, wherein carbon in the complex is used as a carbon source, the carbon is pyrolyzed at high temperature, the separated carbon is used as a reducing agent, ferric ions are reduced into ferrous iron to form ferroferric oxide nano particles, and the ferroferric oxide nano particles gradually react to form a rod-shaped structure in which the ferroferric oxide particles are embedded in the carbon layer along with the rise of the reaction temperature and the prolongation of the time. The pore structure mainly exists between ferroferric oxide particles and inside the nano carbon layer.
The porous ferroferric oxide/carbon nanorod composite material has high saturation magnetic susceptibility (52.6emu/g) and large coercive force Hcj(up to 100.8Oe) which maintains a very high magnetic permeability even in the high frequency range, is a prerequisite for the production of thin electromagnetic wave absorption layers. Experimentally determined resistivity of amorphous carbon is 1 x 104Ω m, much larger than the resistivity of metal magnets (10)-6-10-8Omega m), so that the carbon is coated on the ferroferric oxide nano particles to increase the resistivity of the material and inhibit the eddy current loss, thereby improving the electromagnetic wave absorption performance of the material, wherein the electromagnetic wave absorption frequency range is 2-17.5GHz, and the absorption strength reaches-37.7 dB. Carbon also has the characteristics of light weight and low price, so the nano composite material can be used for preparing a light electromagnetic wave absorber with thin thickness, and has excellent electromagnetic wave absorption performance and important practical application value.
The application of the porous ferroferric oxide/carbon nanorod composite material is used as one of the following materials: 1. electromagnetic shielding in radio communication system, 2, preventing electromagnetic radiation and leakage of high-frequency and microwave heating equipment, 3, constructing microwave dark room, 4, stealth technology.
Further, the application of the porous ferroferric oxide/carbon nano-rod composite material of the invention is that the ferroferric oxide/carbon nano-composite material is mixed with paraffin according to the mass ratio of 40%, the reflection loss of the absorber in the frequency range of 2-17.5GHz is less than-10 decibels (RL < -10dB), namely 90% of electromagnetic waves are absorbed.
Compared with the prior art, the invention has the following excellent effects:
(1) the process for synthesizing the porous ferroferric oxide/carbon nano rod composite material is simple, does not need complex hardware equipment, has no pollution to the environment and has lower manufacturing cost.
(2) The prepared porous ferroferric oxide/carbon nanorod composite material is uniform in particle size and distribution and strong in oxidation resistance and corrosion resistance.
(3) The electromagnetic wave absorber prepared from the composite material has the characteristics of good wave absorbing performance, wide absorbing frequency coverage range, thin absorbing layer thickness and light weight, and can be applied to the fields of electromagnetic radiation and leakage of equipment such as electromagnetic shielding, high frequency and microwave heating prevention, microwave darkroom construction, stealth technology and the like in a radio communication system.
Drawings
FIG. 1 is an XRD diffraction pattern of the precursor obtained in example 1 and an XRD diffraction pattern of a porous ferroferric oxide/carbon nanorod composite material obtained without calcination at temperature.
FIG. 2 is a scanning electron micrograph of the precursor obtained in example 1.
FIG. 3 is a scanning electron microscope image of the porous ferroferric oxide/carbon nanorod composite material obtained in example 1 at different temperatures, wherein a is 500 ℃ and b is 600 ℃.
FIG. 4 is a transmission electron microscope image of the porous ferroferric oxide/carbon nanorod composite material obtained in example 1. Wherein, 1, ferroferric oxide particles, 2, and a nano carbon layer.
FIG. 5 is a magnetic property test curve of the porous ferroferric oxide/carbon nanorod composite material obtained in example 1.
Fig. 6 is an electromagnetic wave absorption curve obtained in example 1.
Fig. 7 is an electromagnetic wave absorption curve obtained in comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example the instrument for measuring the absorption of electromagnetic waves is an Agilent Technologies E8363A electromagnetic wave vector network analyzer.
Example 1:
a porous ferroferric oxide/carbon nanorod composite electromagnetic wave absorber is composed of monodisperse nano-rods with the size of 1.0-1.2 mu m, and the micro-morphology of the porous ferroferric oxide/carbon nanorod composite material is that ferroferric oxide particles are embedded inside a nano-carbon sheet layer.
For FeCl3·6H2O and fumaric acid are used as raw materials for synthesizing a ferroferric oxide precursor, and deionized water is used as a solvent. Mixing the inorganic ferric salt and fumaric acid according to a molar ratio of 1:1, dissolving in deionized water, reacting for 10 hours at 200 ℃ under a closed condition, and washing and drying a product after the reaction is finished to prepare a precursor; and then placing the precursor in a nitrogen atmosphere tube furnace, and preserving the heat at 500 ℃ for 1 hour to prepare the porous ferroferric oxide/carbon nanorod composite material.
The content of carbon and ferroferric oxide in the porous ferroferric oxide/carbon nanorod composite material is respectively 20% and 80% through TG test.
The X-ray powder diffraction pattern (XRD) of the obtained sample (as shown in figure 1) shows that the synthesized porous ferroferric oxide/carbon nanorod composite material is ferroferric oxide with a face-centered cubic structure, and the comparison with standard diffraction data (JCPDS-190629) shows that the purity of the synthesized ferroferric oxide is very high, and carbon has no peak in XRD. The characterization of a Scanning Electron Microscope (SEM) (figure 2) shows that the precursor is a monodisperse nanosheet layer with the length of about 1.0-1.2 microns, and the characterization of the Scanning Electron Microscope (SEM) (figure 3) and a Transmission Electron Microscope (TEM) (figure 4) shows that the synthesized porous ferroferric oxide/carbon nanorod composite material is composed of ferroferric oxide particles and a nanocarbon lamella, and the ferroferric oxide is embedded in the carbon lamella. The particle size of the ferroferric oxide is 40-50 nm. The BET test shows that the pore size of the three-dimensional porous ferroferric oxide/carbon nano composite material is 1-20 nm.
By VSThe results of characterization of the synthesized three-dimensional porous ferroferric oxide/carbon nano composite material sample by the M magnetometer show that the sample has a saturation susceptibility of 52.6emu/g, which is smaller than that of the bulk ferroferric oxide (92emu/g), and a coercive force HcjUp to 100.8Oe, see fig. 5.
An electromagnetic wave absorber was prepared from the porous ferroferric oxide/carbon nanorod composite powder of example 1, and the test experiment was as follows:
mixing the prepared porous ferroferric oxide/carbon nano rod composite material powder with paraffin according to the mass ratio of 40 percent, and pressing the mixture into an annular sample (D)Outer cover×dInner partXh ═ 7 × 3.04 × 2.0mm), relevant parameter μrAndrreflection loss measured by Agilent technologies E8363A electromagnetic wave vector network analyzer is measured by mur、rAbsorption frequency and thickness of the sample. Measuredr' there is a small fluctuation at 3.4-13.2GHz, with a value between 8.2-11.5, after which it slowly decreases to 2.2.r"two resonance peaks at 10.6GHz and 15.9GHz, respectively, are 1.9 and 3.2, respectively. Mu.sr' and mur"both decrease and increase, their variation ranges are 0.5-1.0 and 0-0.4, respectively, the minimum value of their absorption peak is-37.7 dB, the bandwidth of the absorption rate less than-10 dB is 15.5GHz, and their electromagnetic wave absorption curve is shown in figure 6.
Example 2:
as in example 1, except that: when the precursor is prepared, the molar ratio of the added ferric salt to the fumaric acid is 1:2, the porous ferroferric oxide/carbon nanorod composite material is prepared, and Scanning Electron Microscope (SEM) representation shows that the size of the synthesized porous ferroferric oxide/carbon nanorod composite material is 0.6-0.8 mu m.
An X-ray powder diffraction pattern (XRD) shows that the synthesized porous ferroferric oxide/carbon nanorod composite material is ferroferric oxide with a face-centered cubic structure, and comparison with standard diffraction data (JCPDS-190629) shows that the synthesized ferroferric oxide has high purity and carbon has no peak in XRD. The result of characterization of the synthesized porous ferroferric oxide/carbon nanorod composite material sample by using a VSM magnetometer shows that the sample has 58.6emu/gSaturation magnetic susceptibility of (1) and coercive force (H) of 150.2Oecj)。
Example 3:
as described in example 1, except that the temperature of the heat preservation in the nitrogen atmosphere is increased to 600 ℃, the obtained porous ferroferric oxide/carbon nanorod composite material is prepared, and an X-ray powder diffraction pattern (XRD) shows that the synthesized porous ferroferric oxide/carbon nanorod microspheres are ferroferric oxide with a face-centered cubic structure, and comparison with standard diffraction data shows that the purity of the synthesized ferroferric oxide is very high, and carbon has no peak in XRD. The characterization of a Scanning Electron Microscope (SEM) shows that the size of the synthesized porous ferroferric oxide/carbon nano rod composite material is 1.0-1.2 mu m.
Comparative example 1:
the procedure is as described in example 1, except that the incubation temperature is increased to 1000 ℃ during the preparation of the precursor. Scanning Electron Microscope (SEM) characterization showed that no intact rod-like structures were formed, all being large particles.
The X-ray powder diffraction pattern (XRD) shows that the synthesized porous ferroferric oxide/carbon nano rod composite material is iron with a body-centered cubic structure, and the comparison with standard diffraction data shows that the synthesized iron has high purity and carbon has peaks in XRD.
Comparative example 2:
test experiment for preparing electromagnetic wave absorber from acidized porous ferroferric oxide/carbon nanorod composite material
The porous ferroferric oxide/carbon nanorod composite powder prepared in example 1 is dissolved in diluted hydrochloric acid with a certain concentration, and is subjected to acidification treatment, so that only nonmagnetic carbon is left. Then mixing the mixture with paraffin according to the mass ratio of 40 percent and pressing the mixture into a ring-shaped sample (D)Outer cover×dInner partXh ═ 7 × 3.04 × 2.0mm), relevant parameter μrAndrreflection loss measured by Agilent Technologies E8363A electromagnetic wave vector network analyzer is measured by mur、rAbsorption frequency and thickness of the sample. The maximum values of the reflection loss values are all below-10 dB, the absorption performance is poor, and the electromagnetic wave absorption curve is shown in figure 7. Thus, the porous ferroferric oxide/carbon nano rod composite material synthesized by the invention can convert the magnetic field into magnetic fieldThe loss and the dielectric loss are effectively combined, the impedance matching level is improved, and the electromagnetic wave absorption performance is excellent.
Claims (5)
1. A preparation method of a porous ferroferric oxide/carbon nanorod composite electromagnetic wave absorbing material is disclosed, wherein the composite electromagnetic wave absorbing material is multiphase nano composite powder consisting of carbon and ferroferric oxide; wherein, ferroferric oxide particles are embedded in the carbon sheet layer to form a monodisperse nanorod with a porous structure;
the size of the composite electromagnetic wave absorption material is 1.0-1.2 mu m, and the aperture is 1-20 nm;
the size of the ferroferric oxide particles is 40-50 nm;
in the porous ferroferric oxide/carbon nanorod composite material, the mass ratio of carbon to ferroferric oxide is (1-40) to (60-99);
the porous ferroferric oxide/carbon nanorod composite electromagnetic wave absorption material has the saturation magnetic susceptibility of 52.6emu/g and the coercive force Hcj100.8 Oe;
the method comprises the following steps:
(1) taking trivalent inorganic ferric salt and fumaric acid as raw materials of a synthetic ferroferric oxide precursor, and taking deionized water as a solvent; mixing the inorganic ferric salt and fumaric acid according to a molar ratio of 1:1, dissolving in deionized water, reacting for 2-30 hours at the temperature of 100-400 ℃ under a closed condition, and washing and drying a product after the reaction is finished to prepare a precursor;
(2) and (3) placing the precursor in a nitrogen atmosphere tube furnace, and preserving heat for 1-5 hours at 500-1000 ℃ to obtain the porous ferroferric oxide/carbon nanorod composite material.
2. The method as set forth in claim 1, wherein the reaction temperature in the step (1) is 100 ℃ to 200 ℃ and the reaction time is 1 to 10 hours.
3. The preparation method according to claim 1, wherein the molar ratio of the inorganic iron salt to the fumaric acid in the step (1) is 1: 1.
4. The method according to claim 1, wherein the ferric inorganic iron salt in step (1) is ferric chloride hexahydrate.
5. The method as set forth in claim 1, wherein the reaction temperature in the step (2) is 500-900 ℃ and the reaction time is 1-5 hours.
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| CN110164703B (en) * | 2019-06-21 | 2021-07-09 | 江苏科技大学 | Porous Fe3O4/C polyhedral material and preparation method and application thereof |
| CN110418564A (en) * | 2019-07-23 | 2019-11-05 | 天津大学 | The preparation method of carbon nanotube and the three-dimensional carbon absorbing material of metal nanoparticle modification |
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