CN111606325A - Preparation method of graphene-ferrite-based nano functional particles with wave absorbing function - Google Patents
Preparation method of graphene-ferrite-based nano functional particles with wave absorbing function Download PDFInfo
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- CN111606325A CN111606325A CN202010535205.5A CN202010535205A CN111606325A CN 111606325 A CN111606325 A CN 111606325A CN 202010535205 A CN202010535205 A CN 202010535205A CN 111606325 A CN111606325 A CN 111606325A
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Abstract
The invention relates to a preparation method of a graphene-ferrite-based nanometer functional molecule with a wave absorbing function. The method comprises the following steps: mixing graphene and biological protein dispersion liquid, performing ultrasonic dispersion, adding an iron source to obtain a mixed liquid, performing hydrothermal mineralization reaction on the mixed liquid, cooling, washing with water, centrifuging, drying, and calcining the obtained mineralized substance. The method realizes the controllable adjustment of the frequency band and the absorption strength of the wave-absorbing material so as to meet the requirements of different fields.
Description
Technical Field
The invention belongs to the field of functional nano composite material preparation, and particularly relates to a preparation method of a graphene-ferrite-based nano functional particle with a wave absorbing function.
Background
The wave-absorbing functional material has wide application in the fields of national defense, military industry and aerospace. The application of the wave-absorbing material on the invisible airplane enables the airplane to sensitively escape from the search and positioning of the radar, greatly improves the fighting and striking capabilities of the fighter and becomes an important strategic material for national defense and military industry.
With the development of science and technology, novel wave-absorbing materials with thin thickness, light weight, wide absorption frequency band and high absorption strength are urgently needed in the market. As an important composition material of the wave-absorbing material, the wave-absorbing functional particles are key components for determining the performance of the wave-absorbing material.
Chinese patent CN201310408074.4 discloses a preparation method of graphene-ferric oxide nanoparticle composite material, comprising the following steps: dissolving raw materials of graphene oxide and ferric salt in water according to a certain mass ratio, and uniformly mixing; step two, separating the graphene oxide from the liquid mixed in the step one through centrifugation or suction filtration, and cleaning the graphene oxide with water or alcohol; and step three, carrying out heat treatment on the product obtained in the step two in air or oxygen to obtain the graphene-ferric oxide nanoparticle composite material, wherein the ferric salt is one of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate and ferrous sulfate, the heat treatment temperature is 300-1000 ℃, and the heat treatment time is 5 minutes-10 hours.
Compared with the patent of the invention, the graphene-ferric oxide nanocomposite with the special olive-shaped morphology is prepared by using commercial graphene as a raw material (the graphene is obtained by chemically reducing graphene oxide) and using natural fibroin as a template and adopting a milder process (the graphene-ferric oxide nanocomposite can be obtained by only processing at the temperature of below 200 ℃ for 10 hours), and the graphene-ferric oxide nanocomposite is endowed with excellent wave-absorbing performance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a graphene-ferrite-based nano functional molecule with a wave absorbing function, so as to fill the blank in the prior art.
The invention provides a preparation method of a graphene-ferrite-based nano functional particle, which comprises the following steps:
(1) mixing graphene and a biological protein dispersion liquid, performing ultrasonic dispersion, and adding an iron source to obtain a mixed liquid, wherein the mass percentage concentration of the iron source in the mixed liquid is 0.5-1.5%, the mass percentage concentration of the biological protein liquid is 0.005-0.2%, and the mass percentage concentration of the graphene is 0.03-0.15%;
(2) carrying out biological hydrothermal mineralization reaction on the mixed solution obtained in the step (1), cooling, washing with water, centrifuging and drying to obtain a mineralized substance;
(3) the in-situ magnetization process comprises the following steps: and (3) calcining the mineralized substance obtained in the step (2) to obtain the graphene-ferrite-based nano functional particles.
The mass percentage concentration of the biological protein dispersion liquid in the step (1) is 0.1-0.5%.
The mass percentage concentration of the deionized water in the mixed solution in the step (1) is 98.15-99.465%.
The biological protein liquid in the step (1) is silk protein liquid.
And (2) in the step (1), the iron source is ferric trichloride.
The temperature of the biological hydrothermal mineralization reaction in the step (2) is 120-180 ℃, and the time of the biological hydrothermal mineralization reaction is 4-12 h.
In the step (2), the drying temperature is 50-70 ℃, and the drying time is 4-6 h.
The calcination process parameters in the step (2) are as follows: heating from room temperature to 200-.
The invention also provides the graphene-ferrite-based nano-functional particles prepared by the method.
The invention also provides application of the graphene-ferrite-based nano functional particles prepared by the method in a wave-absorbing material.
The invention adopts natural fibroin as a template (not only can establish a reaction template through intermolecular hydrogen bond action, but also can improve the dispersibility of the reacted material), adopts ferric salt as an iron source, adopts graphene as a compound component to design a biological hydrothermal mineralization technology to prepare the graphene-ferrite-based nano wave-absorbing functional sub-material with adjustable bandwidth and strength, and meets the application requirements of wave-absorbing materials in more fields. According to the invention, the wave-absorbing strength and the bandwidth can be changed by adjusting the ratio of the graphene and the iron source and the process, so that the use requirements of different fields are met, and the method has a wide application prospect.
The wave-absorbing material prepared by the invention has excellent wave-absorbing performance and good solvent dispersibility, and can be added into a polymer system by a composite technology for spinning to obtain a fiber product with the wave-absorbing performance; can also be compounded with adhesive or paint to prepare the wave-absorbing functional paint with excellent performance.
Advantageous effects
(1) The invention provides a method for preparing a graphene-ferrite rarefied functional material by a biological hydrothermal mineralization technology.
(2) The invention realizes the controllable adjustment of the frequency band and the absorption strength of the wave-absorbing material so as to meet the requirements of different fields.
(3) The invention prepares the nano composite material with excellent wave absorption performance, and realizes adjustable and controllable wave absorption performance from the source.
(4) The method is different from the reported method, has simple process and can be industrially operated.
(5) The olive-shaped graphene-ferric oxide functional material with the special structure is prepared by taking fibroin as a template, and is beneficial to enhancing the wave-absorbing performance of the material.
(6) The invention adopts commercial graphene as a raw material, and prepares the nano composite material with the wave-absorbing function by a mild process.
Drawings
Fig. 1 is an SEM image of graphene-ferrite nano-functionals prepared in example 2 of the present invention at different magnifications (a, b, c).
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Silk was purchased from heim trade ltd, iron trichloride from national reagents, and commercial graphene from the sixth element of changzhou.
Example 1
Firstly, adding graphene into fibroin dispersion liquid with the mass percentage concentration of 0.1%, and uniformly dispersing under the action of ultrasonic waves; then, mixing ferric trichloride, silk protein liquid and graphene dispersion liquid according to the mass percentage concentration ratio of 0.5% -ferric trichloride (1 g): 0.005% silk protein solution: 0.03% graphene: 99.465% deionized water, and mixing uniformly for use.
And then, filling the reaction mother liquor into a mineralization reaction kettle, reacting for 4 hours at 120 ℃, taking out, and naturally cooling to room temperature. Then washing with water, centrifuging, and finally drying in a vacuum oven at 60 ℃ for 48 hours to obtain the mineralized powder.
Calcining the obtained mineralized powder for a certain time in a programmed heating environment to obtain the magnetic graphene-ferrite-based nano composite functional sub-material with the wave absorbing function, wherein the programmed heating environment is 2 ℃/min for heating from room temperature to 200 ℃ for 1h, then heating to 400 ℃ at 2 ℃/min for heat preservation for 1h, and then naturally cooling to obtain the graphene-ferrite-based nano functional material with the wave absorbing property. The wave absorbing performance of the composite material is tested by a microwave vector instrument, the frequency is tested to be 2-18GHz, and the wave absorbing strength is tested to be-40 dB.
Example 2
Firstly, adding graphene into fibroin dispersion liquid with the mass percentage concentration of 0.5%, and uniformly dispersing under the action of ultrasonic waves; then, ferric trichloride, silk protein liquid and graphene dispersion liquid are mixed according to the mass percentage concentration ratio of 1.5% ferric trichloride (1 g): 0.2% fibroin solution: 0.15% graphene: and (3) uniformly mixing 98.15% of deionized water for later use.
Then the reaction mother liquor is put into a mineralization reaction kettle, reacts for 12 hours at the temperature of 180 ℃, is taken out, and is naturally cooled to the room temperature. Then washing with water, centrifuging, and finally drying in a vacuum oven at 60 ℃ for 48 hours to obtain the mineralized powder.
Calcining the obtained mineralized powder for a certain time in a programmed heating environment to obtain the magnetic graphene-ferrite-based nano composite functional sub-material with the wave absorbing function, wherein the programmed heating environment is 5 ℃/min, the temperature is increased from room temperature to 300 ℃ for 3h, then the temperature is increased to 800 ℃ at 2 ℃/min, the temperature is maintained for 3h, then the temperature is naturally reduced to obtain the graphene-ferrite-based nano functional material with the wave absorbing performance, a microwave vector instrument is adopted to test the wave absorbing performance, the test frequency is 2-18GHz, and the wave absorbing strength is-51 dB.
FIG. 1 shows that: the invention can realize the preparation of the special olive-structured graphene-ferric oxide nanometer functional material through the process conditions, and fig. 1 is a sample prepared in the embodiment 2 of the invention.
Example 3
Firstly, adding graphene into fibroin dispersion liquid with the mass percentage concentration of 0.4%, and uniformly dispersing under the action of ultrasonic waves; then, mixing ferric trichloride, silk protein liquid and graphene dispersion liquid according to the mass percentage concentration ratio of 1% ferric trichloride (1 g): 0.1% fibroin solution: 0.1% graphene: and (3) uniformly mixing 98.8% of deionized water for later use.
Then the reaction mother liquor is put into a mineralization reaction kettle, reacts for 10 hours at the temperature of 160 ℃, is taken out, and is naturally cooled to the room temperature. Then washing with water, centrifuging, and finally drying in a vacuum oven at 60 ℃ for 48 hours to obtain the mineralized powder.
Calcining the obtained mineralized powder for a certain time in a programmed heating environment to obtain the magnetic graphene-ferrite-based nano composite functional sub-material with the wave absorbing function, heating the temperature from room temperature to 250 ℃ at the temperature of 3 ℃/min in the programmed heating environment for 2h, then heating the temperature to 500 ℃ at the temperature of 2 ℃/min for 2h, and then naturally cooling the temperature to obtain the graphene-ferrite-based nano functional material with the wave absorbing performance, testing the wave absorbing performance by using a microwave vector instrument, testing the frequency to be 2-18GHz, and testing the wave absorbing strength to be-44 dB.
Claims (8)
1. A preparation method of graphene-ferrite nano-functional particles comprises the following steps:
(1) mixing graphene and a biological protein dispersion liquid, performing ultrasonic dispersion, and adding an iron source to obtain a mixed liquid, wherein the mass percentage concentration of the iron source in the mixed liquid is 0.5-1.5%, the mass percentage concentration of the biological protein liquid is 0.005-0.2%, and the mass percentage concentration of the graphene is 0.03-0.15%;
(2) carrying out biological hydrothermal mineralization reaction on the mixed solution obtained in the step (1), cooling, washing with water, centrifuging and drying to obtain a mineralized substance;
(3) and (3) calcining the mineralized substance obtained in the step (2) to obtain the graphene-ferrite-based nano functional particles.
2. The method according to claim 1, wherein the mass percentage concentration of the bioprotein dispersion in the step (1) is 0.1% -0.5%; the mass percentage concentration of the deionized water in the mixed solution is 98.15-99.465%.
3. The method according to claim 1, wherein the biological protein fluid in step (1) is a silk protein fluid; the iron source is ferric trichloride.
4. The method as claimed in claim 1, wherein the hydrothermal mineralization reaction temperature in step (2) is 120-180 ℃ and the hydrothermal mineralization reaction time is 4-12 h.
5. The method according to claim 1, wherein the drying temperature in the step (2) is 50-70 ℃ and the drying time is 40-60 h.
6. The method of claim 1, wherein the calcination in step (2) has the following process parameters: heating from room temperature to 200-.
7. A graphene-ferrite-based nano-functional molecule prepared by the method of claim 1.
8. The application of the graphene-ferrite-based nano functional particles prepared by the method of claim 1 in wave-absorbing materials.
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