CN110256847B - Preparation method of polyaniline/carbon foam composite material with controllable wave absorption performance - Google Patents
Preparation method of polyaniline/carbon foam composite material with controllable wave absorption performance Download PDFInfo
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Abstract
The invention relates to a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which comprises the steps of calcining melamine foam, soaking the calcined melamine foam in concentrated sulfuric acid, and drying to obtain carbon foam; dispersing protonic acid and an oxidant in water to obtain a dispersion liquid A; dispersing aniline in water to obtain aniline dispersion liquid, and dispersing aniline in an ice water mixture to obtain dispersion liquid B; and (3) fully absorbing the dispersion liquid B by the carbon foam, then adding the dispersion liquid B into the dispersion liquid A, stirring under an ice/water mixture, filtering out the foam, pre-freezing, and then carrying out vacuum freeze drying to prepare the polyaniline/carbon foam composite material. Compared with the prior art, the composite foam wave-absorbing material has excellent wave-absorbing strength and wider wave-absorbing bandwidth, and has good elasticity, so that the composite foam can deform through external force application to adjust the wave-absorbing performance of the composite foam wave-absorbing material.
Description
Technical Field
The invention relates to a preparation method of a wave-absorbing material, in particular to a preparation method of a polyaniline/carbon foam composite material with controllable wave-absorbing performance.
Background
The carbon foam has a specific pore structure, wherein most pores are connected with each other, and the specific structure enables the carbon foam to have the excellent properties of large specific surface area, light weight, good thermal stability, high thermal conductivity, high electrical conductivity and the like. In addition, the properties of carbon foams are influenced by the properties of the composite contained therein, in addition to the pore structure size, and thus have broader applications than carbon materials of other morphologies. At present, when the carbon foam is applied to the field of wave-absorbing material preparation, the defects of complex preparation mode and small wave-absorbing strength exist.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, and composite foam with adjustable wave absorption strength and wave absorption bandwidth by stress adjustment is prepared by a simple means.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the polyaniline/carbon foam composite material with controllable wave absorption performance comprises the following steps:
calcining clean melamine foam, cooling to room temperature, taking out, soaking in concentrated sulfuric acid, repeatedly washing with deionized water to neutrality, and drying to obtain carbon foam;
fully dispersing protonic acid and an oxidant in water to obtain a dispersion liquid A;
dispersing aniline in water to obtain aniline dispersion liquid, and dispersing the dispersion liquid in an ice water mixture to obtain dispersion liquid B;
and (3) fully absorbing the dispersion liquid B by the carbon foam, then adding the dispersion liquid B into the dispersion liquid A, stirring under an ice/water mixture, filtering out the foam, washing with deionized water and ethanol until the washing liquid is transparent, pre-freezing, and then carrying out vacuum freeze drying to prepare the polyaniline/carbon foam composite material.
The melamine foam is calcined at the temperature of 500-950 ℃ for 1-5 h. The product obtained by low calcination temperature has uneven surface carbonization; if the temperature is too high, the foam is easy to be excessively carbonized, the foam is brittle and loses elasticity, the stress regulation and control cannot be realized, and the resistance is reduced, so that the dielectric loss is reduced, and the wave absorbing performance is weakened.
The melamine foam calcination treatment temperature is preferably 800-900 ℃, and the time is preferably 90-120 min. The carbon foam obtained within the calcining temperature range not only maintains the three-dimensional network skeleton structure, but also has good elasticity, can realize the adjustment of the wave absorption performance by realizing the stress regulation and control of the deformation degree, and simultaneously, the surface is uniformly carbonized, so that the dielectric loss capacity of the carbon foam to electromagnetic waves is improved, and the improvement of the wave absorption performance of the carbon foam is facilitated.
The protonic acid comprises hydrochloric acid, p-toluenesulfonic acid or salicylic acid, and the oxidant comprises ammonium persulfate, ferric chloride or potassium dichromate. The protonic acid has wide source and low cost, and can effectively dope a aniline monomer, so that polyaniline has good conductivity, and the dielectric loss of a system is favorably improved, thereby enhancing the wave-absorbing performance.
The molar ratio of the protonic acid to the oxidant is 0.01-0.8: 0.02-0.1, and the concentration of protonic acid in water is 0.1-8 mol/L.
The protonic acid and the oxidant are ultrasonically dispersed in water, the ultrasonic power is 100-1000W, and the time is controlled to be 10-45 min. Compared with the dispersion modes such as mechanical stirring and the like, the ultrasonic dispersion mixes the liquid materials from a microscopic (molecular level) angle, can more effectively disperse and refine component droplets, and can enable the protonic acid and oxidant droplets to be more finely and fully mixed.
The aniline is dispersed by ultrasonic to form aniline dispersion liquid with the concentration of 0.01-5mol/L, and then dispersed in an ice-water mixture by ultrasonic, the ultrasonic power is 100-1000W, and the time is controlled to be 1-12 min.
The carbon foam is magnetically stirred in the ice/water mixture at a stirring speed of 200-.
Pre-freezing for 1-24h at the temperature of-10 to-90 ℃ during pre-freezing treatment; the vacuum freeze drying is carried out in a vacuum freeze dryer at-8 to-60 ℃ and under the vacuum degree of 1 to 15pa for 1 to 36 hours.
The prepared polyaniline/carbon foam composite material has excellent wave-absorbing strength and wider wave-absorbing bandwidth, has good elasticity, can deform the composite foam through external force application so as to adjust the wave-absorbing performance of the composite foam, and can be used for preparing the polyaniline/carbon foam composite material with controllable wave-absorbing performance, thereby protecting an electronic device from being interfered by electromagnetic waves and normally operating in a required working frequency range. The controllable wave-absorbing material prepared by the invention is beneficial to expanding the application of the wave-absorbing material in the fields of electromagnetic shielding, high-precision national defense war industry and the like. The polyaniline/carbon foam composite material prepared by the invention is in a foam shape and can be used for preparing the field of controllable wave-absorbing materials.
Compared with the prior art, the invention is compounded with polyaniline on the basis of the flexible carbon foam three-dimensional porous network structure, thereby being beneficial to improving the dielectric loss and impedance matching performance of the material and enhancing the wave-absorbing performance of the material. Meanwhile, the wave absorption intensity and the effective wave absorption bandwidth are regulated and controlled by applying different stresses to the polyaniline/carbon foam composite material to change the deformation degree of the polyaniline/carbon foam composite material, so that the stress is controllable. The controllable wave-absorbing property has important significance for widening the practical application field, and has the following advantages:
firstly, the carbon foam prepared by carbonizing the surface of the melamine foam by adopting a high-temperature calcination method not only has a three-dimensional network structure and can increase the reflection of electromagnetic waves inside so as to increase the loss of the electromagnetic waves, but also reduces the surface resistance, is favorable for improving the dielectric loss capability of the carbon foam and is favorable for the polymerization in situ of polyaniline on the surface of the carbon foam.
The wave reflection loss of the polyaniline/carbon foam composite material prepared by the simple in-situ polymerization method can be regulated and controlled between-69.76 dB and-20.49 dB, the effective wave-absorbing bandwidth can be regulated and controlled between 3.10 GHz and 6.25GHz, and compared with the foam wave-absorbing material synthesized by the existing method, the foam wave-absorbing material has light weight and adjustable wave-absorbing performance.
And thirdly, the polyaniline/carbon foam composite material prepared by the invention can be applied to the field of controllable wave-absorbing materials.
Drawings
FIG. 1 is a diagram of the wave-absorbing performance of a polyaniline/carbon foam composite material under the condition of no deformation;
FIG. 2 is a wave-absorbing performance diagram of polyaniline/carbon foam composite material deformed by 15%;
FIG. 3 is a wave-absorbing performance diagram of polyaniline/carbon foam composite deformed by 30%;
FIG. 4 is a wave-absorbing performance diagram of polyaniline/carbon foam composite material deformed by 45%.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention provides a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which comprises the following steps:
(1) preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at the constant temperature of 500 ℃ and 950 ℃ for 1-5h, and then gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 1-50min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at the temperature of 20-50 ℃ for 1-12 h;
(2) preparation of dispersion a: weighing 0.01-0.8 mol of protonic acid and 0.02-0.1mol of oxidant, and adding into 50-360ml of water; carrying out ultrasonic dispersion for 10-45min under the power of 500W to ensure that protonic acid and an oxidant are fully dispersed in water, wherein the used protonic acid is any one of hydrochloric acid, p-toluenesulfonic acid or salicylic acid, and the oxidant is any one of ammonium persulfate, ferric chloride or potassium dichromate;
(3) preparation of dispersion B: ultrasonically dispersing 0.03-0.1mol of aniline (An) in 10-100ml of water to obtain An dispersion liquid, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 300W, and the ultrasonic time is 1-12 min;
(4) preparing a polyaniline/carbon foam composite material: and putting the dried carbon foam into the dispersion liquid A after fully absorbing the dispersion liquid B, and carrying out magnetic stirring for 1-6h at the rotating speed of 200-2000r/min under the ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-50 ℃ for 1-24h, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer for freeze drying for 1-36h to obtain the polyaniline/carbon foam composite material.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1:
the embodiment is a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which is carried out according to the following steps:
(1) preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at 950 deg.C for 2.5h, and gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 15min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at 50 ℃ for 12 h;
(2) preparation of dispersion a: weighing 0.02mol of p-toluenesulfonic acid and 0.02mol of ammonium persulfate into 360ml of water; ultrasonically dispersing for 45min under the power of 500W to fully disperse the protonic acid and the oxidant in water;
(3) preparation of dispersion B: ultrasonically dispersing 0.03mol of aniline (An) in 10ml of water to obtain An dispersion liquid, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 300W, and the ultrasonic time is 12 min;
(4) preparing a polyaniline/carbon foam composite material: after the dried carbon foam had absorbed the dispersion B sufficiently, it was put into the dispersion A and stirred magnetically at a rotational speed of 200r/min for 6 hours under an ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-50 ℃ for 2 hours, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer for freeze drying for 36 hours to obtain the polyaniline/carbon foam composite material.
The carbon foam prepared by carbonizing the surface of the melamine foam by adopting a high-temperature calcination method not only has a three-dimensional network structure and can increase the reflection of electromagnetic waves inside so as to increase the loss of the electromagnetic waves, but also reduces the surface resistance, is favorable for improving the dielectric loss capacity of the carbon foam, is favorable for the polymerization in situ of polyaniline on the surface of the carbon foam, and further improves the loss and absorption of the electromagnetic waves.
The polyaniline/carbon foam composite material prepared by the invention can realize effective loss on more than 90% of electromagnetic waves within the range of 8.70-14.95GHz when the composite foam is not deformed under the condition of 3.5mm thickness under the test frequency, and the wave-absorbing strength reaches the maximum value of-69.76 dB at 12.90 GHz; when the composite foam deforms by 15%, the effective wave-absorbing bandwidth is 9.25-15.50GHz, and the wave-absorbing strength reaches the maximum value of-61.39 dB; when the composite foam deforms by 30%, the effective wave-absorbing bandwidth is 9.05-15.30GHz, and the wave-absorbing strength reaches the maximum value of-28.77 dB; when the composite foam deforms by 45%, the effective wave-absorbing bandwidth is 6.95-10.95GHz, and the wave-absorbing strength reaches the maximum value of-20.49 dB.
The polyaniline/carbon foam composite material prepared by the invention can be applied to the field of controllable wave-absorbing materials.
Example 2:
the embodiment is a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which is carried out according to the following steps:
(1) preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at 950 deg.C for 2.5h, and gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 15min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at 50 ℃ for 12 h;
(2) preparation of dispersion a: weighing 0.3mol of hydrochloric acid and 0.02mol of ammonium persulfate, and adding into 360ml of water; ultrasonically dispersing for 45min under the power of 500W to fully disperse the protonic acid and the oxidant in water;
(3) preparation of dispersion B: ultrasonically dispersing 0.03mol of aniline (An) in 10ml of water to obtain An dispersion liquid, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 300W, and the ultrasonic time is 12 min;
(4) preparing a polyaniline/carbon foam composite material: after the dried carbon foam had absorbed the dispersion B sufficiently, it was put into the dispersion A and stirred magnetically at a rotational speed of 200r/min for 6 hours under an ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-50 ℃ for 2 hours, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer for freeze drying for 36 hours to obtain the polyaniline/carbon foam composite material.
The carbon foam prepared by carbonizing the surface of the melamine foam by adopting a high-temperature calcination method not only has a three-dimensional network structure and can increase the reflection of electromagnetic waves inside so as to increase the loss of the electromagnetic waves, but also reduces the surface resistance, is favorable for improving the dielectric loss capacity of the carbon foam, is favorable for the polymerization in situ of polyaniline on the surface of the carbon foam, and further improves the loss and absorption of the electromagnetic waves.
The polyaniline/carbon foam composite material prepared by the invention can realize the absorption of 90% of electromagnetic waves within the frequency range of 5.6-18GHz when not deformed, and has the lowest value of reflection loss of-40.08 at 13.78GHz when the thickness is 3.0 mm.
The polyaniline/carbon foam composite material prepared by the invention can be applied to the field of controllable wave-absorbing materials.
Example 3:
the embodiment is a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which is carried out according to the following steps:
(1) preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at 950 deg.C for 2.5h, and gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 15min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at 50 ℃ for 12 h;
(2) preparation of dispersion a: weighing 0.3mol of hydrochloric acid and 0.02mol of ammonium persulfate, and adding into 360ml of water; ultrasonically dispersing for 45min under the power of 500W to fully disperse the protonic acid and the oxidant in water;
(3) preparation of dispersion B: ultrasonically dispersing 0.03mol of aniline (An) in 10ml of water to obtain An dispersion liquid, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 300W, and the ultrasonic time is 12 min;
(4) preparing a polyaniline/carbon foam composite material: after the dried carbon foam had absorbed the dispersion B sufficiently, it was put into the dispersion A and stirred magnetically at a rotational speed of 200r/min for 6 hours under an ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-50 ℃ for 2 hours, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer for freeze drying for 36 hours to obtain the polyaniline/carbon foam composite material.
The invention has the advantages that: the carbon foam prepared by carbonizing the surface of the melamine foam by adopting a high-temperature calcination method not only has a three-dimensional network structure and can increase the reflection of electromagnetic waves inside so as to increase the loss of the electromagnetic waves, but also reduces the surface resistance, is favorable for improving the dielectric loss capacity of the carbon foam, is favorable for the polymerization in situ of polyaniline on the surface of the carbon foam, and further improves the loss and absorption of the electromagnetic waves.
The polyaniline/carbon foam composite material prepared by the invention can realize the absorption of 90% of electromagnetic waves within the frequency range of 6.0-18GHz when not deformed, and has the lowest reflection loss value of-47.26 at 9.86GHz when the thickness is 4.0 mm.
The polyaniline/carbon foam composite material prepared by the invention can be applied to the field of controllable wave-absorbing materials.
Example 4:
this embodiment is a method for preparing a polyaniline nanoring wire with wave absorption properties, and is different from embodiment 3 in that: in the step (2), ferric chloride is used as an oxidant, and other steps are the same.
Example 5:
the embodiment is a method for preparing polyaniline nanometer ring line with wave absorption performance, which is different from the embodiment 2 in that: the protonic acid used in step (2) was 0.6mol hydrochloric acid, and the other steps were the same.
Example 6:
the embodiment is a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which is carried out according to the following steps:
(1) preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at 500 deg.C for 5 hr, and gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 15min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at 50 ℃ for 12 h;
(2) preparation of dispersion a: weighing 0.01mol of p-toluenesulfonic acid and 0.05mol of ferric chloride, and adding into water, wherein the concentration of the p-toluenesulfonic acid is controlled to be 0.1 mol/L; carrying out ultrasonic dispersion for 45min under the power of 100W to fully disperse the p-toluenesulfonic acid and the ferric chloride in the water;
(3) preparation of dispersion B: ultrasonically dispersing aniline (An) in water to obtain An dispersion liquid with the concentration of 0.01mol/L, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 100W, and the ultrasonic time is 12 min;
(4) preparing a polyaniline/carbon foam composite material: after the dispersion B was sufficiently absorbed by the dried carbon foam, the dispersion A was put into a magnetic stirrer and stirred for 4 hours at a rotation speed of 400r/min under an ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-10 ℃ for 24 hours, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer, wherein the temperature is controlled to be-8 ℃, and the vacuum degree is 1pa, and freeze-drying the frozen polyaniline/carbon foam for 36 hours to obtain the polyaniline/carbon foam composite material.
Example 7:
the embodiment is a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which is carried out according to the following steps:
(1) preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at the constant temperature of 800 ℃ for 2h, and then gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 15min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at 50 ℃ for 12 h;
(2) preparation of dispersion a: 1mol of salicylic acid and 0.1mol of potassium dichromate are weighed and added into water, and the concentration of p-toluenesulfonic acid is controlled to be 1 mol/L; carrying out ultrasonic dispersion for 30min under the power of 400W to fully disperse the salicylic acid and the potassium dichromate in the water;
(3) preparation of dispersion B: ultrasonically dispersing aniline (An) in water to obtain An dispersion liquid with the concentration of 0.1mol/L, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 300W, and the ultrasonic time is 10 min;
(4) preparing a polyaniline/carbon foam composite material: after the dried carbon foam had absorbed the dispersion B sufficiently, it was put into the dispersion A and stirred magnetically at 500r/min for 3 hours under an ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-20 ℃ for 18 hours, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer, wherein the temperature is controlled to be-20 ℃ and the vacuum degree is 5pa, and freeze-drying the frozen polyaniline/carbon foam for 24 hours to obtain the polyaniline/carbon foam composite material.
Example 8:
the embodiment is a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which is carried out according to the following steps:
(1) preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at 900 deg.C for 90min, and gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 10min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at 50 ℃ for 24 h;
(2) preparation of dispersion a: weighing 8mol of p-toluenesulfonic acid, adding 0.1mol of potassium dichromate into water, and controlling the concentration of the p-toluenesulfonic acid to be 8 mol/L; carrying out ultrasonic dispersion for 10min under the power of 1000W to fully disperse the p-toluenesulfonic acid and the potassium dichromate in water;
(3) preparation of dispersion B: ultrasonically dispersing aniline (An) in water to obtain An dispersion liquid with the concentration of 5mol/L, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 1000W, and the ultrasonic time is 1 min;
(4) preparing a polyaniline/carbon foam composite material: after the dispersion B was sufficiently absorbed by the dried carbon foam, the dispersion A was put into a magnetic stirrer and stirred for 1 hour at 2000r/min under an ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-90 ℃ for 2 hours, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer, wherein the temperature is controlled to be-60 ℃, and the vacuum degree is controlled to be 15pa, and freeze-drying the frozen polyaniline/carbon foam for 1 hour to obtain the polyaniline/carbon foam composite material.
Example 9:
the embodiment is a preparation method of a polyaniline/carbon foam composite material with controllable wave absorption performance, which is carried out according to the following steps:
(1) preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at 950 deg.C for 60min, and gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 10min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at 50 ℃ for 24 h;
(2) preparation of dispersion a: weighing 0.5mol of hydrochloric acid and 0.05mol of potassium dichromate, adding into water, and controlling the concentration of p-toluenesulfonic acid to be 6 mol/L; carrying out ultrasonic dispersion for 30min under the power of 500W to fully disperse hydrochloric acid and potassium dichromate in water;
(3) preparation of dispersion B: ultrasonically dispersing aniline (An) in water to obtain An dispersion liquid with the concentration of 2mol/L, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 500W, and the ultrasonic time is 5 min;
(4) preparing a polyaniline/carbon foam composite material: after the dispersion B was sufficiently absorbed by the dried carbon foam, the dispersion A was put into a magnetic stirrer and stirred for 3 hours at 1000r/min under an ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-60 ℃ for 6 hours, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer, wherein the temperature is controlled to be-40 ℃, and the vacuum degree is 10pa, and freeze-drying the frozen polyaniline/carbon foam for 5 hours to obtain the polyaniline/carbon foam composite material.
Example 10:
the following experiments were used to verify the effect of the present invention:
firstly, preparing carbon foam: the clean melamine foam was calcined in a resistance furnace: calcining at 950 deg.C for 2.5h, and gradually cooling to room temperature. The whole process is carried out under the protection of nitrogen. Cooling the foam to room temperature, taking out the foam, soaking the foam in concentrated sulfuric acid for 15min, repeatedly washing the foam to be neutral by using deionized water, and drying the foam in a vacuum oven at 50 ℃ for 12 h;
secondly, preparing a dispersion liquid A: weighing 0.02mol of p-toluenesulfonic acid and 0.02mol of ammonium persulfate into 360ml of water; ultrasonically dispersing for 45min under the power of 500W to fully disperse the protonic acid and the oxidant in water;
thirdly, preparing a dispersion liquid B: ultrasonically dispersing 0.03mol of aniline (An) in 10ml of water to obtain An dispersion liquid, and ultrasonically dispersing the An dispersion liquid in An ice-water mixture, wherein the ultrasonic power is 300W, and the ultrasonic time is 12 min;
fourthly, preparing the polyaniline/carbon foam composite material: after the dried carbon foam had absorbed the dispersion B sufficiently, it was put into the dispersion A and stirred magnetically at a rotational speed of 200r/min for 6 hours under an ice/water mixture. After completion, the foam was filtered off and washed with deionized water and ethanol until the wash was clear. And finally, pre-freezing the polyaniline/carbon foam (PANI/CF) in a low-temperature refrigerator at the temperature of-50 ℃ for 2 hours, and then placing the frozen polyaniline/carbon foam in a vacuum freeze dryer for freeze drying for 36 hours to obtain the polyaniline/carbon foam composite material which is named as PANI/CF.
An Agilent N5224A is adopted to test the electromagnetic parameters of the polyaniline/carbon foam composite material with wave absorption performance under different deformations, and the electromagnetic parameters are introduced into a wave absorption loss formula to obtain the reflection loss of the polyaniline/carbon foam composite material under different deformation degrees, wherein fig. 1 is a wave absorption performance diagram of PANI/CF under no deformation, fig. 2 is a wave absorption performance diagram of PANI/CF under 15% deformation, fig. 3 is a wave absorption performance diagram of PANI/CF 30% deformation, and fig. 4 is a wave absorption performance diagram of PANI/CF 45% deformation. (wave absorption curves of 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 and 5 in the figure under the analog thickness represented by the corresponding number respectively)
As shown in the figures 1-4, the wave reflection loss of the polyaniline/carbon foam composite material can be regulated and controlled between-69.76 dB and-20.49 dB, and the effective wave-absorbing bandwidth can be regulated and controlled between 3.10 GHz and 6.25 GHz.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. The application of the polyaniline/carbon foam composite material as a material with controllable wave-absorbing performance is characterized in that the wave-absorbing performance is adjusted by adjusting and controlling the deformation degree of the polyaniline/carbon foam composite material through stress;
the preparation method of the polyaniline/carbon foam composite material comprises the following steps:
calcining clean melamine foam at the temperature of 500-800 ℃ for 1-5h, cooling to room temperature, taking out, soaking in concentrated sulfuric acid, repeatedly washing with deionized water to neutrality, and drying to obtain carbon foam;
ultrasonically dispersing protonic acid and an oxidant in water to obtain a dispersion liquid A;
ultrasonically dispersing aniline in water to obtain an aniline dispersion liquid, and ultrasonically dispersing the dispersion liquid in an ice water mixture to obtain a dispersion liquid B;
and (3) fully absorbing the dispersion liquid B by the carbon foam, then adding the dispersion liquid B into the dispersion liquid A, stirring under an ice/water mixture, filtering out the foam, washing with deionized water and ethanol until the washing liquid is transparent, pre-freezing, and then carrying out vacuum freeze drying to prepare the polyaniline/carbon foam composite material.
2. The use of the polyaniline/carbon foam composite material as a material with controllable wave-absorbing properties according to claim 1, characterized in that the melamine foam calcination treatment time is 90-120 min.
3. Use of the polyaniline/carbon foam composite as a material with controllable wave-absorbing properties according to claim 1, characterized in that the protic acid comprises hydrochloric acid, p-toluenesulfonic acid or salicylic acid.
4. Use of the polyaniline/carbon foam composite as a material with controllable wave-absorbing properties according to claim 1, characterized in that the oxidizing agent comprises ammonium persulfate, ferric chloride or potassium dichromate.
5. Use of the polyaniline/carbon foam composite as a material with controllable wave-absorbing properties according to claim 1 or 3 or 4, characterized in that the molar ratio of the protonic acid to the oxidizing agent is 0.01-8: 0.02-0.1, and the concentration of protonic acid in water is 0.1-8 mol/L.
6. The use of the polyaniline/carbon foam composite material as a material with controllable wave-absorbing property as claimed in claim 1, 3 or 4, wherein the protonic acid and the oxidant are ultrasonically dispersed in water, the ultrasonic power is 100-1000W, and the time is controlled within 10-45 min.
7. The use of the polyaniline/carbon foam composite material as a material with controllable wave-absorbing property as claimed in claim 1, wherein aniline is dispersed by ultrasound to form an aniline dispersion liquid with a concentration of 0.01-5mol/L, and then dispersed in an ice-water mixture by ultrasound, the ultrasound power is 100-1000W, and the time is controlled to be 1-12 min.
8. The use of the polyaniline/carbon foam composite material as a material with controllable wave-absorbing properties as claimed in claim 1, wherein the carbon foam is magnetically stirred in an ice/water mixture at a stirring speed of 200-2000rpm for 1-6 h.
9. The use of the polyaniline/carbon foam composite as a material with controllable wave-absorbing properties according to claim 1, characterized in that the pre-freezing treatment is pre-freezing at-10 to-90 ℃ for 1 to 24 hours; the vacuum freeze drying is carried out in a vacuum freeze dryer at-8 deg.C to-60 deg.C and vacuum degree of 1-15Pa for 1-36 h.
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| CN111302826A (en) * | 2020-04-20 | 2020-06-19 | 无锡敬仁电子材料科技有限公司 | Ferrite/carbon composite inorganic foam wave-absorbing material and preparation method thereof |
| CN113136131B (en) * | 2021-03-10 | 2022-05-13 | 大连理工大学 | High-temperature-stability wave-absorbing coating and preparation method and application thereof |
| CN113956532B (en) * | 2021-11-09 | 2022-11-18 | 中国科学院理化技术研究所 | Millimeter wave absorbing material and preparation method and application thereof |
| CN115041144B (en) * | 2022-05-23 | 2024-05-03 | 广州大学 | Polyaniline nitrogen-doped carbon foam, preparation method and application |
| CN115386337B (en) * | 2022-08-12 | 2023-09-08 | 许昌学院 | Chiral polyaniline/biomass derived porous carbon composite wave-absorbing material and preparation method thereof |
| CN115651606B (en) * | 2022-12-14 | 2023-09-19 | 中南大学 | Three-dimensional metal organic framework derivative/carbon foam composite wave-absorbing material and preparation method thereof |
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