CN112745694B - Petroleum asphalt/ferroferric oxide composite wave absorbing agent, preparation method thereof and wave absorbing material - Google Patents
Petroleum asphalt/ferroferric oxide composite wave absorbing agent, preparation method thereof and wave absorbing material Download PDFInfo
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Abstract
The invention provides a petroleum asphalt/ferroferric oxide composite wave absorbing agent, a preparation method thereof and a wave absorbing material, belonging to the technical field of electromagnetic wave absorbing materials. According to the invention, after petroleum asphalt and sodium chloride are pyrolyzed, the obtained pyrolyzed asphalt is a hydrocarbon with rich polycyclic aromatic hydrocarbon and has a porous nano lamellar structure, so that the conductivity of the petroleum asphalt is improved, and then the pyrolyzed asphalt and ferric chloride hexahydrate are subjected to solvothermal reaction, ferroferric oxide nano particles are formed in the solvothermal reaction process, so that the petroleum asphalt can be effectively and stably modified, a good conductive loop is formed between the introduction of the ferroferric oxide nano particles and the pyrolyzed asphalt, and the magnetic loss performance of the composite material is further enhanced.
Description
Technical Field
The invention relates to the technical field of electromagnetic wave-absorbing materials, in particular to a petroleum asphalt/ferroferric oxide composite wave-absorbing agent, a preparation method thereof and a wave-absorbing material.
Background
With the rapid development of modern science and technology, the derived electromagnetic wave radiation has caused many complex problems such as electromagnetic pollution, electromagnetic interference, information disclosure and the like, and the development of the fields such as information industry, electronic industry and the like is hindered; for national defense construction, particularly for the emergence of microwave electronic technology and advanced radar, stealth is taken as an effective means for improving the survival, penetration and depth capabilities of a weapon system, and the stealth is a hot spot in all military strong national corner-to-military advanced fields in the world. Therefore, the development of a material capable of absorbing electromagnetic waves in a specific frequency band is an effective means for solving the problems at present, and has high research value and application prospect.
The petroleum asphalt is used as a byproduct in the petroleum production process, has the characteristics of low cost, large yield and the like, and polycyclic aromatic hydrocarbon contained in the petroleum asphalt makes the conversion into an ideal carbon material possible under certain conditions, thereby having great significance for the research of the petroleum asphalt as a novel wave-absorbing material. At present, the wave-absorbing material prepared by adopting petroleum asphalt has thicker coating, narrower effective wave-absorbing bandwidth and improved wave-absorbing performance.
Disclosure of Invention
The invention aims to provide a petroleum asphalt/ferroferric oxide composite wave absorbing agent, a preparation method thereof and a wave absorbing material.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a petroleum asphalt/ferroferric oxide composite wave absorbent, which comprises the following steps: pyrolyzing a mixture of petroleum asphalt and sodium chloride to obtain pyrolyzed asphalt;
mixing ferric chloride hexahydrate, anhydrous acetate, polyethylene glycol, ethylene glycol and pyrolytic asphalt, and carrying out solvothermal reaction on the obtained mixed solution to obtain the petroleum asphalt/ferroferric oxide composite wave absorbent.
Preferably, the mass ratio of the petroleum asphalt to the sodium chloride is 1: 4.
Preferably, the pyrolysis temperature is 600-1000 ℃, and the time is 6-10 h; the pyrolysis is carried out under the condition of introducing argon.
Preferably, the temperature of the solvothermal reaction is 160-220 ℃, and the time is 6-14 h.
Preferably, the mass of the ferric chloride hexahydrate is converted into a mass of ferroferric oxide, and the mass ratio of the ferroferric oxide to the pyrolytic asphalt is (0.25-1.5): 1.
preferably, the anhydrous acetate salt comprises anhydrous sodium acetate; the dosage ratio of the ferric chloride hexahydrate to the anhydrous acetate to the polyethylene glycol to the ethylene glycol is (0.2-2.0) g to 3.2g to 1g to 40 mL.
Preferably, after the pyrolysis reaction, washing and drying the product of the pyrolysis reaction, wherein the drying temperature is 70-110 ℃, and the drying time is 12-24 h.
Preferably, before the pyrolysis, the method further comprises the step of ball milling the mixture of the petroleum asphalt and the sodium chloride.
The invention provides a petroleum asphalt/ferroferric oxide composite wave absorbent prepared by the preparation method in the scheme, which comprises pyrolytic asphalt and ferroferric oxide nano particles, wherein the pyrolytic asphalt is a hydrocarbon with polycyclic aromatic hydrocarbon and has a porous nano lamellar structure.
The invention provides a wave-absorbing material, which comprises the petroleum asphalt/ferroferric oxide composite wave-absorbing agent and a binder in the scheme; the mass ratio of the petroleum asphalt/ferroferric oxide composite wave absorbing agent to the binder is 1 (4-9).
The invention provides a preparation method of a petroleum asphalt/ferroferric oxide composite wave absorbent, which comprises the following steps: pyrolyzing a mixture of petroleum asphalt and sodium chloride to obtain pyrolyzed asphalt; mixing ferric chloride hexahydrate, anhydrous acetate, polyethylene glycol, ethylene glycol and pyrolytic asphalt, and carrying out solvothermal reaction on the obtained mixed solution to obtain the petroleum asphalt/ferroferric oxide composite wave absorbent.
According to the invention, after petroleum asphalt and sodium chloride are pyrolyzed, the obtained pyrolyzed asphalt is a hydrocarbon with rich polycyclic aromatic hydrocarbon and has a porous nano lamellar structure, so that the conductivity of the petroleum asphalt is improved, and then the pyrolyzed asphalt and ferric chloride hexahydrate are subjected to solvothermal reaction, ferroferric oxide nano particles are formed in the solvothermal reaction process, so that the petroleum asphalt can be effectively and stably modified, a good conductive loop is formed between the introduction of the ferroferric oxide nano particles and the pyrolyzed asphalt, and the magnetic loss performance of the composite material is further enhanced.
The results of the examples show that the dielectric constant of the wave-absorbing material prepared by the petroleum asphalt/ferroferric oxide composite wave-absorbing agent prepared by the invention is as follows: the real part is 26.94-3.32, and the imaginary part is 27.69-0.63; magnetic permeability: the real part is 1.35-0.88, and the imaginary part is 0.08-0.40; the reflection loss is-14 to-70 dB; the effective absorption bandwidth is 1.12-5.12 GHz; the thickness of the material is 1.1-6 mm; the composite wave-absorbing material has good wave-absorbing performance, can effectively reduce the thickness of a material coating and enlarge the range of effective wave-absorbing bandwidth.
Drawings
FIG. 1 is an SEM image of a pyrolysis pitch of comparative example 1;
FIG. 2 is an SEM image of a petroleum asphalt/ferroferric oxide composite wave absorbent prepared in example 3;
FIG. 3 is PA-Fe of example 43O4-1.5 PA-Fe from example 33O4-1.0 PA-Fe of example 23O40.5 and PA-Fe of comparative example 13O4-an XRD pattern of 0;
FIG. 4 is a graph showing the impedance matching changes of the wave-absorbing materials prepared in application examples 2-4 and comparative application example 1.
Detailed Description
The invention provides a preparation method of a petroleum asphalt/ferroferric oxide composite wave absorbent, which comprises the following steps: pyrolyzing a mixture of petroleum asphalt and sodium chloride to obtain pyrolyzed asphalt;
mixing ferric chloride hexahydrate, anhydrous acetate, polyethylene glycol, ethylene glycol and pyrolytic asphalt, and carrying out solvothermal reaction on the obtained mixed solution to obtain the petroleum asphalt/ferroferric oxide composite wave absorbent.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The invention pyrolyzes the mixture of petroleum asphalt and sodium chloride to obtain the pyrolyzed asphalt.
In the present invention, the mass ratio of the petroleum asphalt to the sodium chloride is preferably 1: 4. Prior to pyrolysis, the present invention preferably ball mills the mixture of petroleum pitch and sodium chloride. In the invention, the time for ball milling is preferably 8-10 h. The invention preferably performs the ball milling under dry milling conditions. The invention has no special requirement on the rotation speed of the ball milling, and the rotation speed of the ball milling which is well known in the field can be adopted. The petroleum asphalt is hard, and the ball milling can be used for fully crushing the petroleum asphalt to finally obtain uniform powder, thereby being beneficial to the implementation of the pyrolysis reaction.
In the invention, the pyrolysis temperature is preferably 600-1000 ℃, more preferably 700-900 ℃, and further preferably 750-850 ℃; the pyrolysis time is preferably 6-10 hours, and more preferably 7-9 hours. In the pyrolysis process, the petroleum asphalt is cracked, and the cracked asphalt is in a porous nanosheet structure under the action of the template agent sodium chloride, so that the polycyclic aromatic hydrocarbon structure of the asphalt is more fully exposed and is effectively compounded with ferroferric oxide.
In the present invention, the pyrolysis is preferably carried out under the condition of passing argon gas. According to the invention, through introducing argon in the pyrolysis process, on one hand, the pyrolysis asphalt is prevented from being oxidized, on the other hand, impurities generated in the experimental process are taken away, and meanwhile, the stability of the whole pyrolysis temperature can be ensured.
After the pyrolysis is completed, the invention preferably further comprises washing and drying the product of the pyrolysis reaction to obtain the pyrolysis asphalt. The invention removes sodium chloride by water washing. In the invention, the drying temperature is preferably 70-110 ℃, and more preferably 80-100 ℃; the drying time is preferably 12-24 hours, and more preferably 15-20 hours.
After obtaining the pyrolytic asphalt, the invention mixes ferric chloride hexahydrate, anhydrous acetate, polyethylene glycol, ethylene glycol and pyrolytic asphalt, and carries out solvothermal reaction on the obtained mixed solution to obtain the petroleum asphalt/ferroferric oxide composite wave absorbent.
In the present invention, the anhydrous acetate is preferably anhydrous sodium acetate. The polyethylene glycol is preferably polyethylene glycol-2000 or polyethylene glycol-4000, more preferably polyethylene glycol-2000.
In the present invention, the amount ratio of ferric chloride hexahydrate, anhydrous acetate, polyethylene glycol and ethylene glycol is preferably (0.2-2.0) g:3.2g:1g:40mL, more preferably (0.5-1.6) g:3.2g:1g:40mL, and most preferably 1.05g:3.2g:1g:40 mL. In the invention, the mass of the ferric chloride hexahydrate is converted into the mass of ferroferric oxide, and the mass ratio of the ferroferric oxide to the pyrolytic asphalt is preferably (0.25-1.5): 1, more preferably (0.5 to 1.25): 1, most preferably 1:1.
In the invention, the ferric chloride hexahydrate is used as a source of iron in ferroferric oxide; the anhydrous acetate salt provides acetate which reacts with hydrogen ions in the water, and the hydroxide ions in the water react with ferric ions to form Fe (OH)3(ii) a The polyethylene glycol is used as a dispersing agent, so that agglomeration of ferroferric oxide generated in a solvothermal process is avoided; the ethylene glycol can ensure the uniformity of the size and the shape of the generated ferroferric oxide nano particles as much as possible.
In the present invention, the mixing process is preferably: adding ferric chloride hexahydrate, anhydrous acetate, polyethylene glycol and pyrolytic asphalt into ethylene glycol, and stirring to obtain a mixed solution. In the invention, the stirring time is preferably 60-180 min, and more preferably 80-150 min; the stirring temperature is preferably 60-90 ℃, and more preferably 70-80 ℃.
The invention preferably pours the obtained mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and then transfers the mixed solution into a high-temperature drying oven for solvent thermal reaction.
In the invention, the temperature of the solvothermal reaction is preferably 160-220 ℃, more preferably 170-210 ℃, and most preferably 180-200 ℃; the solvothermal reaction time is preferably 6-14 h, and more preferably 8-12 h.
In the process of the solvothermal reaction, ferric chloride hexahydrate generates nano ferroferric oxide particles under the action of acetate, and meanwhile, the nano ferroferric oxide particles play a role in modifying the pyrolytic asphalt.
After the solvothermal reaction is finished, the method preferably further comprises washing and drying a solvothermal reaction product system to obtain the petroleum asphalt/ferroferric oxide composite wave absorbent. In the present invention, the washing is preferably performed by washing and suction-filtering a plurality of times using absolute ethanol and ultrapure water. In the invention, the drying temperature is preferably 55-85 ℃, and more preferably 60-80 ℃; the drying time is preferably 12-24 hours, and more preferably 15-20 hours.
The invention provides a petroleum asphalt/ferroferric oxide composite wave absorbent prepared by the preparation method in the scheme, which comprises pyrolytic asphalt and ferroferric oxide nano particles, wherein the pyrolytic asphalt is a hydrocarbon with polycyclic aromatic hydrocarbon and has a porous nano lamellar structure.
In the invention, the ferroferric oxide nanoparticles are preferably spherical, and the particle size is preferably 20-120 nm, more preferably 40-100 nm.
In the invention, the mass ratio of the pyrolytic asphalt to the ferroferric oxide nanoparticles is preferably (0.25-1.5): 1, more preferably (0.5 to 1.25): 1, most preferably 1:1.
According to the invention, the petroleum asphalt sheet layer is modified by the nano ferroferric oxide particles, and the conductive loop formed between the ferroferric oxide and the petroleum asphalt sheet layer is favorable for improving the wave absorbing performance of the wave absorbing agent.
The invention provides a wave-absorbing material, which comprises the petroleum asphalt/ferroferric oxide composite wave-absorbing agent and a binder in the scheme; the mass ratio of the petroleum asphalt/ferroferric oxide composite wave absorbing agent to the binder is 1 (4-9), and preferably 1: 4. In the present invention, the binder preferably includes paraffin wax.
The petroleum asphalt/ferroferric oxide composite wave absorbing agent, the preparation method thereof and the wave absorbing material provided by the invention are explained in detail with reference to the following examples, but the invention is not to be construed as being limited by the scope of protection.
The petroleum asphalt used in the following examples and comparative examples was derived from petroleum asphalt provided by the Ministry of Gansu of Petroleum of China; ferric chloride hexahydrate is from chemical reagents of Mimi Europe, Inc. of Tianjin; anhydrous sodium acetate was obtained from metropolis congon chemicals ltd; ethylene glycol was from Tianjin Lianlong Bohua pharmaceutical chemistry, Inc.; polyethylene glycol-2000 was from Dougenk Chemicals, Inc.; the sodium chloride is from Tianjin Lianlong Bohua pharmaceutical chemistry, Inc.
Example 1
Weighing 0.5g of powdered petroleum asphalt and 2g of sodium chloride, pouring the two kinds of powder into a ball milling tank, carrying out ball milling for 9 hours under a dry milling condition, taking out the powder after the ball milling is finished, transferring the powder into a tubular furnace for pyrolysis at 900 ℃, introducing Ar gas in the whole experiment process, closing an instrument after the experiment is finished, naturally cooling the whole equipment to room temperature, and taking out the powder;
repeatedly washing the obtained powder with deionized water, then placing the powder in a drying box for drying treatment at the temperature of 80 ℃ for 18h, and drying to obtain the pyrolytic asphalt;
3.2g of anhydrous sodium acetate, 1g of polyethylene glycol-2000, 0.26g of ferric chloride hexahydrate and 300mg of pyrolytic asphalt are weighed and dispersed into a beaker filled with 40mL of ethylene glycol, the mixture is fully stirred for 2 hours at the temperature of 80 ℃, then the uniformly stirred solution is poured into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the high-pressure reaction kettle is transferred into a high-temperature drying box to carry out solvothermal reaction for 8 hours, the reaction temperature is set to be 180 ℃, and the reaction kettle is taken out after the reaction time is over and the reaction kettle is naturally cooled. Washing and filtering the obtained mixed solution for multiple times by using absolute ethyl alcohol and ultrapure water, then placing the mixed solution into a drying box for drying treatment, setting the temperature at 75 ℃, drying for 18 hours, and obtaining the petroleum asphalt/ferroferric oxide composite wave absorbing agent after drying, wherein the mass ratio of the pyrolytic asphalt to the ferroferric oxide is 1:0.25 and is marked as PA-Fe3O4-0.25。
Example 2
Weighing 0.5g of powdered petroleum asphalt and 2g of sodium chloride, pouring the two kinds of powder into a ball milling tank, carrying out ball milling for 9 hours under a dry milling condition, taking out the powder after the ball milling is finished, transferring the powder into a tubular furnace for pyrolysis at 900 ℃, introducing Ar gas in the whole experiment process, closing an instrument after the experiment is finished, naturally cooling the whole equipment to room temperature, and taking out the powder;
repeatedly washing the obtained powder with deionized water, then placing the powder in a drying box for drying treatment at the temperature of 80 ℃ for 18h, and drying to obtain the pyrolytic asphalt;
3.2g of anhydrous sodium acetate, 1g of polyethylene glycol-2000, 0.52g of ferric chloride hexahydrate and 300mg of pyrolytic asphalt are weighed and dispersed into a beaker containing 40mL of ethylene glycol, the mixture is fully stirred for 2 hours at the temperature of 80 ℃, and then the mixture is stirredPouring the uniformly mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, then transferring the solution into a high-temperature drying oven for solvothermal reaction, setting the reaction time to be 8 hours and the reaction temperature to be 180 ℃, and taking out the reaction kettle after the reaction time is over and the reaction kettle is naturally cooled. Washing and filtering the obtained mixed solution for multiple times by using absolute ethyl alcohol and ultrapure water, then placing the mixed solution into a drying box for drying treatment, setting the temperature at 75 ℃, drying for 18 hours, and obtaining the petroleum asphalt/ferroferric oxide composite wave absorbent after drying, wherein the mass ratio of the pyrolytic asphalt to the ferroferric oxide is 1:0.5 and is marked as PA-Fe3O4-0.5。
Example 3
Weighing 0.5g of powdered petroleum asphalt and 2g of sodium chloride, pouring the two kinds of powder into a ball milling tank, carrying out ball milling for 9 hours under a dry milling condition, taking out the powder after the ball milling is finished, transferring the powder into a tubular furnace for pyrolysis at 900 ℃, introducing Ar gas in the whole experiment process, closing an instrument after the experiment is finished, naturally cooling the whole equipment to room temperature, and taking out the powder;
repeatedly washing the obtained powder with deionized water, then placing the powder in a drying box for drying treatment at the temperature of 80 ℃ for 18h, and drying to obtain the pyrolytic asphalt;
3.2g of anhydrous sodium acetate, 1g of polyethylene glycol-2000, 1.05g of ferric chloride hexahydrate and 300mg of pyrolytic asphalt are weighed and dispersed into a beaker filled with 40mL of ethylene glycol, the mixture is fully stirred for 2 hours at the temperature of 80 ℃, then the uniformly stirred solution is poured into a high-pressure reaction kettle with polytetrafluoroethylene as a lining, the high-pressure reaction kettle is transferred into a high-temperature drying box to carry out solvothermal reaction for 8 hours, the reaction temperature is set to be 180 ℃, and the reaction kettle is taken out after the reaction time is over and the reaction kettle is naturally cooled. Washing and filtering the obtained mixed solution for multiple times by using absolute ethyl alcohol and ultrapure water, then placing the mixed solution into a drying box for drying treatment, setting the temperature at 75 ℃, drying for 18 hours, and obtaining the petroleum asphalt/ferroferric oxide composite wave absorbent after drying, wherein the mass ratio of the pyrolytic asphalt to the ferroferric oxide is 1:1 and is marked as PA-Fe3O4-1.0。
Example 4
Weighing 0.5g of powdered petroleum asphalt and 2g of sodium chloride, pouring the two kinds of powder into a ball milling tank, carrying out ball milling for 9 hours under a dry milling condition, taking out the powder after the ball milling is finished, transferring the powder into a tubular furnace for pyrolysis at 900 ℃, introducing Ar gas in the whole experiment process, closing an instrument after the experiment is finished, naturally cooling the whole equipment to room temperature, and taking out the powder;
repeatedly washing the obtained powder with deionized water, then placing the powder in a drying box for drying treatment at the temperature of 80 ℃ for 18h, and drying to obtain the pyrolytic asphalt;
3.2g of anhydrous sodium acetate, 1g of polyethylene glycol-2000, 1.57g of ferric chloride hexahydrate and 300mg of pyrolytic asphalt are weighed and dispersed into a beaker filled with 40mL of ethylene glycol, the mixture is fully stirred for 2 hours at the temperature of 80 ℃, then the uniformly stirred solution is poured into a high-pressure reaction kettle with polytetrafluoroethylene as a lining, the high-pressure reaction kettle is transferred into a high-temperature drying box to carry out solvothermal reaction for 8 hours, the reaction temperature is set to be 180 ℃, and the reaction kettle is taken out after the reaction time is over and the reaction kettle is naturally cooled. Washing and filtering the obtained mixed solution for multiple times by using absolute ethyl alcohol and ultrapure water, then placing the mixed solution into a drying box for drying treatment, setting the temperature at 75 ℃, drying for 18 hours, and obtaining the petroleum asphalt/ferroferric oxide composite wave absorbent after drying, wherein the mass ratio of the pyrolytic asphalt to the ferroferric oxide is 1:1.5 and is marked as PA-Fe3O4-1.5。
Comparative example 1
Weighing 0.5g of powdered petroleum asphalt and 2g of sodium chloride, pouring the two kinds of powder into a ball milling tank, carrying out ball milling for 9 hours under a dry milling condition, taking out the powder after the ball milling is finished, transferring the powder into a tubular furnace for pyrolysis at 900 ℃, introducing Ar gas in the whole experiment process, closing an instrument after the experiment is finished, naturally cooling the whole equipment to room temperature, and taking out the powder;
repeatedly washing the obtained powder with deionized water, then placing the powder in a drying oven for drying at 80 ℃ for 18h to obtain the pyrolytic asphaltIs marked as PA-Fe3O4-0。
Comparative example 2
The difference from example 1 is that petroleum asphalt is not pyrolyzed, and a wave absorbing agent is prepared as in example 1.
Structural characterization:
1. SEM observation of the pyrolytic asphalt of comparative example 1 is shown in FIG. 1. As can be seen from fig. 1, the pyrolytic pitch has a porous nanosheet structure.
2. For PA-Fe prepared in example 33O4-1.0, as shown in fig. 2, the result of SEM observation shows that the petroleum asphalt/ferroferric oxide composite wave absorbing agent is formed by compounding a porous carbon nanosheet layer and spherical ferroferric oxide particles, as can be seen from fig. 2.
3. For PA-Fe3O4-1.5、PA-Fe3O4-1.0、PA-Fe3O4-0.5 and PA-Fe3O4XRD characterization of-0 showed the result in FIG. 3, and it can be seen from FIG. 3 that PA-Fe3O4-0 shows a diffraction peak of the graphitized structure after the pyrolysis treatment, indicating the formation of graphitization. The rest three substances except the diffraction peak containing graphite all have the diffraction peak of ferroferric oxide, which shows the formation of the ferroferric oxide, and the intensity of the characteristic diffraction peak of the ferroferric oxide is enhanced along with the increase of the content of the ferroferric oxide.
Application examples 1 to 4
The composite wave absorbing agent of the embodiments 1 to 4 and solid paraffin are mixed according to the mass ratio of 1:4, and then the ring is fully pressed to obtain a ring-shaped sample with the inner diameter of 3.04mm and the outer diameter of 7.00mm, namely the wave absorbing material of the application examples 1 to 4.
Application example 5
The composite wave absorbing agent in example 3 and solid paraffin were mixed in a mass ratio of 1:9, and then subjected to sufficient compression to obtain a ring-shaped sample with an inner diameter of 3.04mm and an outer diameter of 7.00mm, that is, the wave absorbing material of application example 5.
Comparative application example 1
And (3) mixing the composite wave absorbing agent in the comparative example 1 with solid paraffin according to the mass ratio of 1:4, and fully pressing a ring to obtain the ring-shaped wave absorbing material with the inner diameter of 3.04mm and the outer diameter of 7.00 mm.
Comparative application example 2
And (3) mixing the composite wave absorbing agent in the comparative example 2 with solid paraffin according to the mass ratio of 1:4, and fully pressing a ring to obtain the ring-shaped wave absorbing material with the inner diameter of 3.04mm and the outer diameter of 7.00 mm.
And (3) performance testing:
the performance of the wave-absorbing materials of application examples 1-5 and comparative application examples 1-2 was tested by using a vector network analyzer model N5232B, produced by Agilent (KEYSIGHT), at a test frequency of 2-18 GHz, and the results are shown in Table 1.
TABLE 1 wave-absorbing Material compositions and wave-absorbing Properties of the wave-absorbing materials
Comparing the real part of the dielectric constant of the wave-absorbing material obtained in application example 2: 2.88 ~ 2.52, imaginary part: 0.41 to 0.04; real part of magnetic permeability: 1.09-0.91, imaginary part: 0.04 to-0.08; minimum reflection loss: 2.19dB, corresponding to frequency: 18 GHz; the thickness of the corresponding material is as follows: 3.3 mm. The result shows that the petroleum asphalt/ferroferric oxide composite material obtained without pyrolysis of the petroleum asphalt has almost no wave-absorbing performance.
As can be seen from table 1, the addition of ferroferric oxide and pyrolytic asphalt in a proper proportion greatly improves the wave-absorbing performance of the wave-absorbing material, but as the proportion of the ferroferric oxide and the pyrolytic asphalt is continuously increased, spherical ferroferric oxide cannot fully modify a petroleum asphalt sheet layer, the agglomeration phenomenon of more ferroferric oxide nanoparticles is aggravated, the dispersibility is reduced, a conductive loop formed between the ferroferric oxide and the petroleum asphalt sheet layer is hindered, and the wave-absorbing performance of the whole composite material is inhibited; when the mass ratio of the pyrolytic asphalt to the ferroferric oxide is 1:1 and the mass ratio of the wave absorbing agent to the paraffin is 1:4, the reflection loss of the obtained wave absorbing material reaches the maximum value, and the thickness of the coating of the material is the thinnest (namely, the application example 3). The results of application examples 5 and 1 show that the mass ratio of the wave absorbing agent to the binder also has a certain influence on the wave absorbing performance of the wave absorbing material, and when the mass ratio of the wave absorbing agent to the binder is 1: and 4, the wave-absorbing material has the best wave-absorbing property.
In addition, the wave-absorbing materials prepared in application examples 2, 3 and 4 and comparative application example 1 were subjected to impedance matching test by measuring dielectric and magnetic conductivity of the materials with a vector network analyzer and calculating the formula
The result, Z, is calculatedinI.e. impedance matching of the material, with the ordinate Z ═ Z in fig. 4in/Z0When Z isinAnd Z0The closer the value of (A) is, i.e. Zin/Z0The closer the ratio of (A) to (B) is to 1, the better the impedance matching of the material is, and the better the wave absorbing performance is. It can be seen from fig. 4 that the impedance matching changes corresponding to several wave-absorbing materials are shown, and it can be seen from fig. 4 that the wave-absorbing material with ferroferric oxide introduced is higher than the wave-absorbing material prepared by pyrolysis asphalt, which indicates that the wave-absorbing performance of the petroleum asphalt material without ferroferric oxide added (compare with application example 1) is not outstanding.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a petroleum asphalt/ferroferric oxide composite wave absorbent comprises the following steps: pyrolyzing a mixture of petroleum asphalt and sodium chloride to obtain pyrolyzed asphalt;
mixing ferric chloride hexahydrate, anhydrous acetate, polyethylene glycol, ethylene glycol and pyrolytic asphalt, and carrying out solvothermal reaction on the obtained mixed solution to obtain the petroleum asphalt/ferroferric oxide composite wave absorbent.
2. The method according to claim 1, wherein the mass ratio of the petroleum asphalt to the sodium chloride is 1: 4.
3. The preparation method according to claim 1, wherein the pyrolysis temperature is 600-1000 ℃ and the time is 6-10 h; the pyrolysis is carried out under the condition of introducing argon.
4. The preparation method according to claim 1, wherein the temperature of the solvothermal reaction is 160-220 ℃ and the time is 6-14 h.
5. The preparation method according to claim 1, wherein the mass of the ferric chloride hexahydrate is converted into the mass of ferroferric oxide, and the mass ratio of the ferroferric oxide to the pyrolytic asphalt is (0.25-1.5): 1.
6. the method of claim 1, wherein the anhydrous acetate salt comprises anhydrous sodium acetate; the dosage ratio of the ferric chloride hexahydrate to the anhydrous acetate to the polyethylene glycol to the ethylene glycol is (0.2-2.0) g to 3.2g to 1g to 40 mL.
7. The preparation method of claim 1, further comprising washing and drying the pyrolysis reaction product after the pyrolysis reaction, wherein the drying temperature is 70-110 ℃, and the drying time is 12-24 h.
8. The method of claim 1, further comprising ball milling the mixture of petroleum pitch and sodium chloride prior to pyrolysis.
9. The petroleum asphalt/ferroferric oxide composite wave absorbent prepared by the preparation method of any one of claims 1 to 8 comprises pyrolytic asphalt and ferroferric oxide nanoparticles, wherein the pyrolytic asphalt is a hydrocarbon with polycyclic aromatic hydrocarbon and has a porous nanosheet structure.
10. A wave-absorbing material, which is characterized by comprising the petroleum asphalt/ferroferric oxide composite wave-absorbing agent of claim 9 and a binder; the mass ratio of the petroleum asphalt/ferroferric oxide composite wave absorbing agent to the binder is 1 (4-9).
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| "多孔碳材料的制备及其电磁波吸收性能的研究";刘志;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20171015(第10期);第B015-31页 * |
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