CN111154258A - Ternary nano composite material capable of adjusting wave absorption performance and preparation method thereof - Google Patents
Ternary nano composite material capable of adjusting wave absorption performance and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of wave-absorbing materials, in particular to a ternary nano composite material with adjustable wave-absorbing performance. The final product of the composite material comprises the following single-phase materials in percentage by mass: 10-30% of reduced graphene oxide, 10-60% of polyaniline and the balance of ferroferric oxide; the wave-absorbing material is obtained by carrying out low-temperature polymerization reaction on reduced graphene oxide-ferroferric oxide binary nano particles and aniline, and the wave-absorbing performance of a corresponding ternary nano composite material can be regulated and controlled by changing the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to the aniline; the comparative research on the wave-absorbing performance finds that: along with the increase of the content of polyaniline, the wave-absorbing strength of the corresponding ternary nanocomposite is gradually improved, and the wave-absorbing frequency bandwidth is also greatly increased. Has wide application prospect in the fields of stealth materials, electromagnetic safety protection and the like.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a ternary nano composite material with adjustable wave-absorbing performance.
Background
With the rapid development of the electronic industry and the wide application of electronic products, the electromagnetic wave pollution phenomenon is visible everywhere in daily life, which not only reduces the service life of the electronic products, but also causes certain harm to the living environment of human beings. Therefore, electromagnetic wave absorbing materials have become a research focus of great social attention.
The ferrite wave-absorbing material is low in price, simple in preparation process, high in magnetic conductivity and high in resistivity in a high-frequency band, electromagnetic waves can easily enter a medium and can be attenuated quickly, and the ferrite wave-absorbing material is a mature magnetic loss wave-absorbing material. However, as the novel wave-absorbing material is developed in the direction of 'thin thickness, light weight, strong absorption and wide frequency band', the single traditional ferrite material has limited further development in the wave-absorbing field due to the defects of large density and narrow wave-absorbing frequency band.
Graphene is a novel two-dimensional carbon material, and has the characteristics of high thermal conductivity coefficient, high dielectric constant, high electron mobility, ultra-large specific surface area and the like due to the unique two-dimensional layered structure, and the characteristics enable the graphene to be used as a dielectric loss material to be applied to the field of wave absorption and to be widely concerned in various fields. If the binary composite material obtained by compounding the material with a ferrite material has double wave-absorbing mechanisms of dielectric loss, magnetic loss and the like, the method is an effective method for improving the electromagnetic wave absorption performance of the material.
Conductive polymers are the most representative dielectric loss materials. The graphene-ferrite binary material has the advantages of high electrical loss, low density, good mechanical property, easiness in preparation and the like, and if the graphene-ferrite binary material is introduced into the graphene-ferrite binary material, the impedance matching degree of the composite material is further improved, the absorption frequency band is widened, and the density of the composite material is reduced.
The applicant of the present application filed chinese patent application No. 201810193826.2' graphene ferrite polymer ternary nano composite wave-absorbing material and a preparation method thereof in 2018, 3, 9, the composite wave-absorbing material is graphene nano powder in which a conductive polymer is uniformly coated with ferrite nano particles, and the chemical components of the composite wave-absorbing material are expressed by mass percent: 10-30% of reduced graphene oxide, 20-40% of ferrite nano particles and the balance of conductive polymer. The preparation method comprises the steps of reduction assembly reaction and polymerization reaction; however, the technical scheme obtains approximately fixed wave-absorbing performance, and if the wave-absorbing performance needs to be adjusted, a plurality of technological parameters need to be adjusted, and the process is relatively complex.
Disclosure of Invention
One purpose of the invention is to provide a graphene-ferroferric oxide-polyaniline ternary nanocomposite material with adjustable wave absorption performance, and the composite material can achieve the purpose of adjusting wave absorption strength and wave absorption frequency bandwidth by adjusting the content ratio of the graphene-ferroferric oxide binary material to aniline.
The invention also aims to provide a preparation method of the graphene-ferroferric oxide-polyaniline ternary nanocomposite material with adjustable wave absorption performance.
In order to achieve the purpose, the invention provides the following technical scheme:
a graphene-ferroferric oxide-polyaniline ternary nano composite material with adjustable wave absorption performance comprises the following single-phase materials in percentage by mass in a final product of the composite material: 10-30% of reduced graphene oxide, 10-60% of polyaniline and the balance of ferroferric oxide; the composite material is obtained by carrying out low-temperature polymerization reaction on reduced graphene oxide-ferroferric oxide binary nanoparticles and aniline, the wave absorbing performance of the corresponding ternary nanocomposite material can be regulated and controlled by changing the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to the aniline, and the regulation range of the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to the aniline is 1: 0.5-3.
The wave-absorbing performance of the composite material is wave-absorbing strength and/or wave-absorbing frequency band.
The composite material is prepared by the following steps: (1) preparing graphene-ferroferric oxide binary composite material powder, (2) preparing a graphene-ferroferric oxide-polyaniline ternary composite material; the change of the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to the aniline is realized in the step (2).
When the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to aniline is adjusted within the range of 1: 1-3, and the matching thickness is 3mm, the minimum reflection loss is-23.3 dB to-31 dB, the corresponding wave-absorbing frequency is 7.5GHz to 9GHz, and the frequency bandwidth with the reflection loss value lower than-10 dB is 2GHz to 3.5 GHz.
A preparation method of a graphene-ferroferric oxide-polyaniline ternary nanocomposite material with adjustable wave absorption performance comprises the following steps:
(1) preparing graphene-ferroferric oxide binary composite material powder: ultrasonically dispersing 1-2.5 mol/L ferric chloride and 0.5-1 mol/L ferrous chloride in graphene oxide aqueous dispersion, fully mixing, slowly adding 1-1.5 mol/L ammonia water, maintaining the pH value at 10, keeping stirring for 1.5-3.5 hours, adding 10-15 ml hydrazine hydrate, reacting for 4-6 hours at the temperature of 80-120 ℃ by adopting a water/solvent heat or coprecipitation method, and centrifuging, washing, vacuum drying and grinding the obtained product to obtain graphene nano powder with ferroferric oxide particles dotted, namely the reduced graphene oxide-ferroferric oxide binary composite material;
(2) preparing a graphene-ferroferric oxide-polyaniline ternary composite material: dispersing 0.3-0.6 g of reduced graphene oxide-ferroferric oxide binary composite nanopowder into 40-60 ml of deionized water, and slowly dripping 2-20 g of dodecylbenzene sulfonic acid and 0.2-2 g of aniline after the nanopowder is fully dissolved; keeping the temperature at-1-3 ℃, slowly dropwise adding a deionized water solution in which 0.5-4 g of ammonium persulfate is dissolved after ultrasonic stirring for 25-40 minutes, continuously stirring for 4-5 hours, adding equivalent isopropanol, continuously stirring for 20-40 minutes, performing centrifugal separation, washing with distilled water and ethanol to be neutral, and performing vacuum drying to obtain the graphene-ferroferric oxide-polyaniline ternary nano composite wave-absorbing material with different content ratios;
in the step (2), the wave absorbing performance of the corresponding ternary nanocomposite is regulated and controlled by changing the content ratio of the reduced graphene oxide-ferroferric oxide binary composite to aniline, and the regulation range of the content ratio of the reduced graphene oxide-ferroferric oxide binary composite to aniline is 1: 0.5-3.
In the step (2), the higher the polyaniline content in the final product is, the lower the minimum reflection loss peak value of the composite material is, and the larger the corresponding absorption frequency bandwidth is.
In the step (1): the molar ratio of the ferric chloride to the ferrous chloride is 1-2: 1, the concentration of the graphene oxide aqueous dispersion is 1.0-10 mg/mL, and the size of the ferroferric oxide nano-particles is 10-30 nm.
In the step (2): the vacuum drying temperature is preferably 50-65 ℃ and the time is 40-50 hours.
The invention has the following advantages:
1. through research, the inventor of the application finds that the wave absorbing performance of the corresponding ternary nanocomposite can be adjusted by adjusting the content ratio (the adjustment range is 1: 0.5-3) of the graphene-ferroferric oxide binary material and aniline, and a plurality of process parameters are not required to be adjusted. According to the invention, with the increase of the proportion of polyaniline in the ternary nanocomposite, the wave-absorbing strength of the graphene-ferroferric oxide-polyaniline ternary nanocomposite is improved, and the corresponding wave-absorbing frequency band is greatly widened. Particularly, when the content ratio of the graphene-ferroferric oxide binary composite material to the aniline is 1:3 (namely, a sample 4), the thickness of the corresponding ternary composite material coating is the thinnest (3mm), the reflection loss peak value is the lowest (-31dB), and the corresponding wave-absorbing frequency band is the widest (3.5GHz), so that the composite wave-absorbing material is an ideal composite wave-absorbing material and has wide application prospect.
2. In the composite wave-absorbing material, the graphene surface defects and residual oxygen-containing functional groups are easy to generate polarization relaxation and electric dipole relaxation under the action of an external electric field, and the impedance matching of the single-phase wave-absorbing material can be improved by combining the graphene surface defects and the residual oxygen-containing functional groups with ferrite particles with a magnetic loss mechanism.
3. In the preparation method, the polyaniline introduced on the basis of the graphene-ferroferric oxide binary material can effectively expand the electromagnetic wave absorption range through in-situ polymerization reaction, and the corresponding ternary composite wave-absorbing material can be dissolved in an organic solvent and has better processing performance.
4. The material can be applied to the fields of stealth materials, electromagnetic safety protection and the like; the related materials have wide sources, low price, simple preparation method, excellent wave-absorbing performance and wider application prospect.
Drawings
Fig. 1 is an XRD chart of the 4 graphene-ferroferric oxide-polyaniline ternary nanocomposite materials with different raw material content ratios, prepared in step (2) of examples 1 to 4.
FIGS. 2 to 4 are TEM images of the ternary nanocomposite wave-absorbing material at different magnification ratios, wherein the content ratio of the graphene-ferroferric oxide binary material to aniline is 1:1 (i.e., sample 2).
Fig. 5 is a wave-absorbing performance diagram of the graphene-ferroferric oxide-polyaniline ternary nanocomposite material prepared in the step (2) in example 1.
Fig. 6 is a wave-absorbing performance diagram of the graphene-ferroferric oxide-polyaniline ternary nanocomposite material prepared in the step (2) in example 2.
Fig. 7 is a wave-absorbing performance diagram of the graphene-ferroferric oxide-polyaniline ternary nanocomposite material prepared in the step (2) in example 3.
Fig. 8 is a wave-absorbing performance diagram of the graphene-ferroferric oxide-polyaniline ternary nanocomposite material prepared in the step (2) in example 4.
FIG. 9 is a comparison graph of wave-absorbing properties of 4 graphene-ferroferric oxide-polyaniline ternary nanocomposite materials with different raw material content ratios under the thickness of 3 mm.
Detailed Description
The following description will further explain embodiments of the present invention by referring to the figures and examples, but the present invention is not limited to these examples. In the experimental methods of the following examples, unless otherwise specified, they are conventional methods; the materials used in the examples were purchased from conventional chemical agents, unless otherwise specified.
The graphene-ferroferric oxide-polyaniline ternary nano composite wave-absorbing material with adjustable wave-absorbing performance comprises the following single-phase materials in percentage by mass in the final product of the composite material: 10-30% of reduced graphene oxide, 10-60% of polyaniline and the balance of ferroferric oxide; the composite wave-absorbing material adjusts the wave-absorbing performance of a corresponding ternary nano composite material by changing the content ratio of a reduced graphene oxide-ferroferric oxide binary composite material to aniline, wherein the adjustment range of the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to aniline is 1: 0.5-3.
A preparation method of a graphene-ferroferric oxide-polyaniline ternary nano composite wave-absorbing material with adjustable wave-absorbing performance comprises the following specific steps:
(1) preparing graphene-ferroferric oxide binary composite material powder: ultrasonically dispersing 1-2.5 mol/L ferric chloride and 0.5-1 mol/L ferrous chloride in graphene oxide aqueous dispersion, fully mixing, slowly adding 1-1.5 mol/L ammonia water, and maintaining the pH value at 10. Keeping stirring for 1.5-3.5 hours, adding 10-15 ml of hydrazine hydrate, reacting for 4-6 hours at the temperature of 80-120 ℃ by adopting a water/solvent heat or coprecipitation method, centrifuging, washing, vacuum drying and grinding the obtained product to obtain graphene nano powder decorated with ferroferric oxide particles, namely the reduced graphene oxide-ferroferric oxide binary composite material;
(2) preparing a graphene-ferroferric oxide-polyaniline ternary composite material: dispersing 0.3-0.6 g of reduced graphene oxide-ferroferric oxide binary composite nanopowder into 40-60 ml of deionized water, and slowly dripping 2-20 g of dodecylbenzene sulfonic acid and 0.2-2 g of aniline after the nanopowder is fully dissolved; keeping the temperature at-1-3 ℃, slowly dropwise adding a deionized water solution in which 0.5-4 g of ammonium persulfate is dissolved after ultrasonic stirring for 25-40 minutes, continuously stirring for 4-5 hours, adding equivalent isopropanol, continuously stirring for 20-40 minutes, performing centrifugal separation, washing with distilled water and ethanol to be neutral, and performing vacuum drying to obtain the graphene-ferroferric oxide-polyaniline ternary nano composite wave-absorbing material with different content ratios;
in the step (2), the wave absorbing performance of the corresponding ternary nanocomposite is adjusted by changing the content ratio of the reduced graphene oxide-ferroferric oxide binary composite to aniline, wherein the adjustment range of the content ratio of the reduced graphene oxide-ferroferric oxide binary composite to aniline is 1: 0.5-3.
Wherein the molar ratio of the ferric ions to the ferrous ions in the step (1) is 1-2: 1. The concentration of the graphene oxide aqueous dispersion in the step (1) is 1.0-10 mg/mL. The size of the ferroferric oxide nano particles in the step (1) is 10-30 nm. In the step (2), the preferable vacuum drying temperature is 50-65 ℃, and the time is 40-50 hours
Various embodiments of the invention are described below:
example 1 content ratio of graphene-ferroferric oxide binary material to aniline is 1:0.5
(1) Preparing graphene-ferroferric oxide binary composite material powder: ultrasonically dispersing 1.5mol/L ferric chloride and 1mol/L ferrous chloride in 100mL of graphene oxide aqueous dispersion with the concentration of 5mg/L, slowly adding 1mol/L ammonia water after full dissolution, and maintaining the pH value of the mixed solution at 10. After stirring was maintained for 3 hours, 10ml of hydrazine hydrate was added, the temperature of the solution was raised to 80 ℃, the temperature was maintained and stirring was maintained for 5 hours. And naturally cooling after the reaction is finished, and centrifuging, washing, vacuum drying and grinding the obtained product to obtain the ferroferric oxide particle decorated graphene nano powder.
(2) Preparing a graphene-ferroferric oxide-polyaniline ternary composite material: dispersing 0.5g of graphene-ferroferric oxide binary nano powder into 50ml of deionized water, and slowly dripping 2.5g of dodecylbenzene sulfonic acid and 0.25g of aniline after the graphene-ferroferric oxide binary nano powder is fully dissolved. During this time, the temperature of the mixed solution was maintained at 0 ℃ and the ultrasonic agitation was carried out for 30 minutes. Then, 50ml of a solution containing 0.67g of ammonium persulfate was slowly dropped into the above mixed solution. Keeping the temperature unchanged, continuously stirring for 5 hours, adding 100ml of isopropanol, continuously stirring for 30 minutes, performing centrifugal separation, sequentially washing with distilled water and ethanol to be neutral, and drying in a vacuum drying furnace at 60 ℃ for 48 hours to obtain the graphene-ferroferric oxide binary material and the ternary nano composite wave-absorbing material (namely the sample 1) with the polyaniline content ratio of 1: 0.5.
Example 2 content ratio of graphene-ferroferric oxide binary material to aniline is 1:1
(1) Preparing graphene-ferroferric oxide binary composite powder: ultrasonically dispersing 1.5mol/L ferric chloride and 1mol/L ferrous chloride in 100mL of graphene oxide aqueous dispersion with the concentration of 5mg/L, slowly adding 1mol/L ammonia water after fully dissolving, and maintaining the pH value of the mixed solution at 10. After stirring was maintained for 3 hours, 10ml of hydrazine hydrate was added, the temperature of the solution was raised to 80 ℃, the temperature was maintained and stirring was maintained for 5 hours. And naturally cooling after the reaction is finished, and centrifuging, washing, vacuum drying and grinding the obtained product to obtain the ferroferric oxide particle decorated graphene nano powder.
(2) Preparing a graphene-ferroferric oxide-polyaniline ternary composite material: dispersing 0.5g of graphene-ferroferric oxide binary nano powder into 50ml of deionized water, and slowly dripping 5g of dodecylbenzene sulfonic acid and 0.5g of aniline after the graphene-ferroferric oxide binary nano powder is fully dissolved. During this time, the temperature of the mixed solution was maintained at 0 ℃ and the ultrasonic agitation was carried out for 30 minutes. And then slowly dropping 50ml of solution containing 1.225g of ammonium persulfate into the mixed solution, keeping the temperature unchanged, continuously stirring for 5 hours, adding 100ml of isopropanol, continuously stirring for 30 minutes, performing centrifugal separation, sequentially washing with distilled water and ethanol to be neutral, and drying in a vacuum drying furnace at 60 ℃ for 48 hours to obtain the graphene-ferroferric oxide binary material and the ternary nano composite wave-absorbing material (namely the sample 2) with the polyaniline content ratio of 1: 1.
Example 3 content ratio of graphene-ferroferric oxide binary material to aniline 1:2
(1) Preparing graphene-ferroferric oxide binary composite powder: ultrasonically dispersing 1.5mol/L ferric chloride and 1mol/L ferrous chloride in 100mL of graphene oxide aqueous dispersion with the concentration of 5mg/L, slowly adding 1mol/L ammonia water after full dissolution, and maintaining the pH value of the mixed solution at 10. After stirring was maintained for 3 hours, 10ml of hydrazine hydrate was added, the temperature of the solution was raised to 80 ℃, the temperature was maintained and stirring was maintained for 5 hours. And naturally cooling after the reaction is finished, and centrifuging, washing, vacuum drying and grinding the obtained product to obtain the ferroferric oxide particle decorated graphene nano powder.
(2) Preparing a graphene-ferroferric oxide-polyaniline ternary composite material: dispersing 0.5g of graphene-ferroferric oxide binary nano powder into 50ml of deionized water, and slowly dripping 10g of dodecylbenzene sulfonic acid and 1g of aniline after fully mixing. During this time, the temperature of the mixed solution was maintained at 0 ℃ and the ultrasonic agitation was carried out for 30 minutes. And then slowly dropping 50ml of solution containing 2.5g of ammonium persulfate into the mixed solution, keeping the temperature unchanged, continuously stirring for 5 hours, adding 100ml of isopropanol, continuously stirring for 30 minutes, performing centrifugal separation, sequentially washing with distilled water and ethanol to be neutral, and drying in a vacuum drying furnace at 60 ℃ for 48 hours to obtain the graphene-ferroferric oxide binary material and the ternary nano composite wave-absorbing material (namely the sample 3) with the polyaniline content ratio of 1: 2.
Example 4 content ratio of graphene-ferroferric oxide binary material to aniline is 1:3
(1) Preparing graphene-ferroferric oxide binary composite powder: ultrasonically dispersing 1.5mol/L ferric chloride and 1mol/L ferrous chloride in 100mL of graphene oxide aqueous dispersion with the concentration of 5mg/L, slowly adding 1mol/L ammonia water after full dissolution, and maintaining the pH value of the mixed solution at 10. After stirring was maintained for 3 hours, 10ml of hydrazine hydrate was added, the temperature of the solution was raised to 80 ℃, the temperature was maintained and stirring was maintained for 5 hours. And naturally cooling after the reaction is finished, and centrifuging, washing, vacuum drying and grinding the obtained product to obtain the ferroferric oxide particle decorated graphene nano powder.
(2) Preparing a graphene-ferroferric oxide-polyaniline ternary composite material: dispersing 0.5g of graphene-ferroferric oxide binary nano powder into 50ml of deionized water, and slowly dripping 15g of dodecylbenzene sulfonic acid and 1.5g of aniline after fully mixing. During this time, the temperature of the mixed solution was maintained at 0 ℃ and the ultrasonic agitation was carried out for 30 minutes. And then slowly dripping 50ml of solution containing 3.7g of ammonium persulfate into the mixed solution, keeping the temperature unchanged, continuously stirring for 5 hours, adding 100ml of isopropanol, continuously stirring for 30 minutes, performing centrifugal separation, sequentially washing with distilled water and ethanol to be neutral, and drying in a vacuum drying furnace at 60 ℃ for 48 hours to obtain the graphene-ferroferric oxide binary material and the ternary nano composite wave-absorbing material (namely a sample 4) with the polyaniline content ratio of 1: 3.
Fig. 1 is an XRD chart of the graphene-ferroferric oxide-polyaniline ternary nanocomposite wave-absorbing material prepared in step (2) of examples 1 to 4 with 4 different raw material content ratios. As can be seen, the XRD curves of the 4 samples substantially coincide. Wherein, a characteristic peak of polyaniline appears between 15 and 30 degrees of a 2 theta value range, which indicates that the polyaniline is successfully introduced into the ternary composite material; and obvious characteristic peaks of the ferroferric oxide exist within the range of the 2 theta value of 30-90 degrees, which shows that the ferroferric oxide particles in 4 samples are not damaged.
FIGS. 2 to 4 are TEM images of the ternary nanocomposite wave-absorbing material at different magnification ratios, wherein the content ratio of the graphene-ferroferric oxide binary material to aniline is 1:1 (i.e., sample 2). In the figure, the diameter of the nano particles attached to the graphene sheet layer is about 15nm, obvious lattice fringes are formed, and the lattice spacing is calculated to be 0.253nm and is the same as the lattice spacing corresponding to the (311) crystal face of ferroferric oxide, which indicates that the nano particles are ferroferric oxide nano particles and corresponds to the conclusion in the XRD diagram of a sample. In the figure, polyaniline is a three-dimensional network structure and is coated on the graphene-ferroferric oxide binary composite material.
Fig. 5 to 8 are graphs of the wave-absorbing performance of the 4 graphene-ferroferric oxide-polyaniline ternary nanocomposite wave-absorbing materials prepared in the step (2) of the embodiment 1 to 4 and having different raw material content ratios. Weighing 0.044g of ternary composite sample and 0.066g of paraffin according to the mass ratio of the ternary composite material to the paraffin of 2:3, heating to melt, uniformly stirring, naturally cooling, pressing into a mold to prepare a circular sample with the outer ring diameter of 7mm and the inner ring diameter of 3mm, wherein the thickness of the circular sample is 2.6mm, and performing wave-absorbing performance test on the sample by using a vector network analyzer of the model N5230C in the frequency range of 2-18 GHz by using a coaxial method. As can be seen from FIG. 5, the thickness of the coating of sample 1 is 4mm, the minimum reflection loss value is-17.4 dB when the wave-absorbing frequency is 6.4GHz, the bandwidth with the reflection loss value lower than-10 dB is 1.4GHz, and the wave-absorbing performance is not ideal. As can be seen from fig. 6 (fig. 7 and 8), when the matching thickness is 3mm, the minimum reflection loss of sample 2 (sample 3 and sample 4) is-23.3 dB (-28.2dB and-31 dB), and the corresponding wave-absorbing frequencies are 7.5GHz (7.9GHz and 9 GHz). The frequency bandwidths having reflection loss values lower than-10 dB are 2GHz (2.6GHz and 3.5 GHz).
FIG. 9 is a comparison graph of wave-absorbing properties of 4 graphene-ferroferric oxide-polyaniline ternary nanocomposite materials with different raw material content ratios under the thickness of 3 mm. It can be seen that, as the content of polyaniline increases, the minimum reflection loss peak values of the four composite materials also gradually decrease, and the corresponding absorption frequency bandwidths thereof greatly increase. Particularly, when the content ratio of the graphene-ferroferric oxide binary composite material to the polyaniline is 1:3 (namely, a sample 4), the thickness of the corresponding ternary composite material coating is the thinnest (3mm), the reflection loss peak value is the lowest (-31dB), and the corresponding wave-absorbing frequency band is the widest (3.5 GHz).
The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the protection scope of the invention.
Claims (8)
1. A graphene-ferroferric oxide-polyaniline ternary nanocomposite material with adjustable wave absorption performance is characterized in that: the final product of the composite material comprises the following single-phase materials in percentage by mass: 10-30% of reduced graphene oxide, 10-60% of polyaniline and the balance of ferroferric oxide; the composite material is obtained by carrying out low-temperature polymerization reaction on reduced graphene oxide-ferroferric oxide binary nanoparticles and aniline, the wave absorbing performance of the corresponding ternary nanocomposite material can be regulated and controlled by changing the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to the aniline, and the regulation range of the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to the aniline is 1: 0.5-3.
2. The composite material of claim 1, wherein: the wave-absorbing performance of the composite material is wave-absorbing strength and/or wave-absorbing frequency band.
3. The composite material of claim 1, wherein: the composite material is prepared by the following steps: (1) preparing graphene-ferroferric oxide binary composite material powder, (2) preparing a graphene-ferroferric oxide-polyaniline ternary composite material; the change of the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to the aniline is realized in the step (2).
4. The composite material of claim 1, wherein: when the content ratio of the reduced graphene oxide-ferroferric oxide binary composite material to aniline is adjusted within the range of 1: 1-3, and the matching thickness is 3mm, the minimum reflection loss is-23.3 dB to-31 dB, the corresponding wave-absorbing frequency is 7.5GHz to 9GHz, and the frequency bandwidth with the reflection loss value lower than-10 dB is 2GHz to 3.5 GHz.
5. The preparation method of the graphene-ferroferric oxide-polyaniline ternary nanocomposite material with adjustable wave absorption performance according to claim 1, which is characterized by comprising the following steps:
(1) preparing graphene-ferroferric oxide binary composite material powder: ultrasonically dispersing 1-2.5 mol/L ferric chloride and 0.5-1 mol/L ferrous chloride in graphene oxide aqueous dispersion, fully mixing, slowly adding 1-1.5 mol/L ammonia water, maintaining the pH value at 10, keeping stirring for 1.5-3.5 hours, adding 10-15 ml hydrazine hydrate, reacting for 4-6 hours at the temperature of 80-120 ℃ by adopting a water/solvent heat or coprecipitation method, and centrifuging, washing, vacuum drying and grinding the obtained product to obtain graphene nano powder with ferroferric oxide particles dotted, namely the reduced graphene oxide-ferroferric oxide binary composite material;
(2) preparing a graphene-ferroferric oxide-polyaniline ternary composite material: dispersing 0.3-0.6 g of reduced graphene oxide-ferroferric oxide binary composite nanopowder into 40-60 ml of deionized water, and slowly dripping 2-20 g of dodecylbenzene sulfonic acid and 0.2-2 g of aniline after the nanopowder is fully dissolved; keeping the temperature at-1-3 ℃, slowly dropwise adding a deionized water solution in which 0.5-4 g of ammonium persulfate is dissolved after ultrasonic stirring for 25-40 minutes, continuously stirring for 4-5 hours, adding equivalent isopropanol, continuously stirring for 20-40 minutes, performing centrifugal separation, washing with distilled water and ethanol to be neutral, and performing vacuum drying to obtain the graphene-ferroferric oxide-polyaniline ternary nano composite wave-absorbing material with different content ratios;
in the step (2), the wave absorbing performance of the corresponding ternary nanocomposite is regulated and controlled by changing the content ratio of the reduced graphene oxide-ferroferric oxide binary composite to aniline, and the regulation range of the content ratio of the reduced graphene oxide-ferroferric oxide binary composite to aniline is 1: 0.5-3.
6. The method of claim 5, wherein: in the step (2), the higher the polyaniline content is, the lower the minimum reflection loss peak value of the composite material is, and the larger the corresponding absorption frequency bandwidth is.
7. The method of claim 5, wherein: in the step (1): the molar ratio of the ferric chloride to the ferrous chloride is 1-2: 1, the concentration of the graphene oxide aqueous dispersion is 1.0-10 mg/mL, and the size of the ferroferric oxide nano-particles is 10-30 nm.
8. The method of claim 5, wherein: in the step (2): the vacuum drying temperature is preferably 50-65 ℃ and the time is 40-50 hours.
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