CN116332162A - Honeycomb CNT/TiO 2 Composite material, preparation method and application thereof - Google Patents

Honeycomb CNT/TiO 2 Composite material, preparation method and application thereof Download PDF

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CN116332162A
CN116332162A CN202310181627.0A CN202310181627A CN116332162A CN 116332162 A CN116332162 A CN 116332162A CN 202310181627 A CN202310181627 A CN 202310181627A CN 116332162 A CN116332162 A CN 116332162A
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车仁超
赵彪
张金仓
张捷
程一峰
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Zhejiang Lab
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
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    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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Abstract

The invention discloses a honeycomb CNT/TiO 2 Composite materials, methods of making and uses thereof. The honeycomb CNT/TiO 2 The preparation method of the composite material comprises the following steps: step 1: tiO is prepared by using absolute ethyl alcohol as dispersing agent 2 Dispersion, CNT dispersion, and polystyrene microsphere dispersion; dispersing the polystyrene microsphere dispersion liquid and TiO 2 Mixing the solution and the mixed solution of the CNT dispersion liquid together and performing ultrasonic treatment to obtain a mixed solution; step 2: filtering the mixed solution by using a suction filter to form a film; step 3: drying the film obtained in the step 2; step 4: carrying out high-temperature treatment on the dried sample film obtained in the step 3 by using a vacuum tube furnace to obtain honeycomb CNT/TiO 2 A composite material. The invention provides the honeycomb CNT/TiO 2 Composite materialAs an application of the electromagnetic wave absorbing material, the composite material exhibits excellent wave absorbing performance.

Description

Honeycomb CNT/TiO 2 Composite material, preparation method and application thereof
Technical Field
The invention belongs to the technical field of electromagnetic wave absorbing materials, and particularly relates to a honeycomb CNT/TiO 2 Composite material and preparation method thereofMethods and applications as electromagnetic wave absorbing materials.
Background
Along with the development of microwave communication technology, the application of electronic equipment is very popular, electromagnetic wave pollution is caused, electromagnetic wave pollution has a great influence on human bodies, and airport flights can not take off due to electromagnetic wave interference; in hospitals, mobile phones often interfere with the proper operation of various electronic medical instruments. Meanwhile, in the military field, along with the rapid advance of modern military technologies, the massive use of centimetre wave radars (0.2-40 GHz in the frequency range of microwaves) has severely challenged the viability of military targets and the burst protection capability of weapon systems. Therefore, the research and development of the novel wave-absorbing material has important significance for national defense construction of China and social life of people. It has been reported that various kinds of nanocarbons such as carbon fibers, carbon nanotubes, carbon nanocoils, carbon nanowires, carbon spheres, graphene, reduced graphene oxide, and the like have been successfully prepared, and the corresponding microwave absorption properties have been studied. However, carbon materials alone, which have relatively high conductivity and dielectric loss, are detrimental to impedance matching based on impedance matching and often result in microwave reflection at the surface rather than absorption.
The carbon nano tube has good wave absorbing property from visible light to infrared wave band, and the carbon nano tube and TiO 2 After the composite, the wave absorbing performance can be enhanced, PS balls are used as templates, and after firing, the honeycomb porous structure CNT/TiO is formed 2 Composite material with single CNT or TiO 2 In contrast, the incident electromagnetic wave is due to CNT/TiO 2 Is attenuated by the polarization loss and is trapped in the honeycomb structure, and generally results in higher wave absorbing effect due to multiple reflections between the inner walls of the honeycomb structure. The honeycomb structure improves electromagnetic interference and attenuates incident electromagnetic waves. Thus, honeycomb CNT/TiO 2 The composite material can increase the repeated reflection and absorption of electromagnetic waves in the composite material, has excellent electromagnetic wave absorption effect and is lighter in weight. Thus, carbon nanotubes and TiO with good absorption capacity 2 Compounding into a cellular porous architecture is an effective way to increase the absorptive capacity.
Disclosure of Invention
The invention aims to provide a honeycomb CNT/TiO 2 Composite materials, methods for their preparation and their use as electromagnetic wave absorbing materials.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a honeycomb CNT/TiO 2 The preparation method of the composite material comprises the following steps:
step 1: tiO with the concentration of 1-4 mg/ml is prepared by using absolute ethyl alcohol as dispersing agent 2 A dispersion, a CNT dispersion having a concentration of (1-4) mg/ml, and a Polystyrene (PS) microsphere dispersion having a concentration of (1-4) mg/ml; dispersing the Polystyrene (PS) microsphere dispersion and TiO 2 Mixing the dispersion liquid and the CNT dispersion liquid according to the volume ratio of 3-5:3-5:3-10, and performing ultrasonic treatment to obtain a mixed dispersion liquid;
step 2: filtering the mixed dispersion liquid by a suction filter to form a film;
step 3: transferring the sample film obtained in the step (2) after suction filtration into a blast drying box for drying;
step 4: heating the dried sample film obtained in the step 3 to 400-550 ℃ at a heating rate of 5-10 ℃/min in Ar atmosphere by using a vacuum tube furnace, and preserving heat for 1-3 hours to obtain the honeycomb CNT/TiO 2 A composite material.
In the invention, the TiO 2 Is nano-scale TiO 2 The average particle diameter is preferably between 10 and 30nm, and the crystal phase is mainly in an anatase structure.
In the present invention, the CNT may be commercially available.
In the present invention, the Polystyrene (PS) microspheres are preferably uniform-sized, average spherical diameter of 0.2 to 3 μm, which can be prepared by referring to the existing literature or commercially available ones.
In step 1 of the present invention, ultrasound-assisted solute dissolution may be used. Preferably, the TiO 2 The dispersion liquid and the CNT dispersion liquid are ultrasonic for 45-60 min, and the Polystyrene (PS) microsphere dispersion liquid is ultrasonic for 15-30 min, so that the dispersion is uniform.
Preferably, in step 1, tiO 2 The concentration of the dispersion was 2mg/ml, the concentration of the CNT dispersion was 1mg/ml, and the concentration of the Polystyrene (PS) microsphere dispersion was 2mg/ml.
Preferably, a dispersion of Polystyrene (PS) microspheres and TiO 2 The mixing volume ratio of the dispersion liquid and the CNT dispersion liquid is 3:5:3-10. Further preferable are Polystyrene (PS) microsphere dispersions and TiO 2 The mixing volume ratio of the dispersion liquid and the CNT dispersion liquid is 3:5:8-10.
Preferably, in the step 3, the working temperature of the blast drying box is 50-70 ℃ and the drying time is 6-10 h.
Preferably, in step 4, a vacuum tube furnace is used, and the temperature is raised to 500 ℃ and maintained for 2 hours in an Ar atmosphere at a heating rate of 10 ℃/min.
In a second aspect, the present invention provides a honeycomb CNT/TiO according to the preparation method of the first aspect 2 A composite material.
The composite material prepared by the invention is prepared from carbon nano tube and TiO attached on the surface of the carbon nano tube 2 Particle composition, sample with microporous structure, tiO 2 The particles are mainly of anatase crystal structure.
In a third aspect, the present invention provides the honeycomb CNT/TiO 2 The application of the composite material as an electromagnetic wave absorbing material. The honeycomb CNT/TiO is 2 The minimum reflection loss value of the composite wave-absorbing material is-34.8 dB.
Compared with the prior art, the invention has the beneficial effects that:
(1) CNT is a material with unique one-dimensional material properties, huge performance-controllable working surface, good electrical conductivity and special boundary effect, and thus is widely used in the preparation of wave-absorbing materials; the titanium dioxide is not very excellent in performance, has low dielectric loss capacity and no magnetic loss capacity, and has good wave absorbing performance only when being compounded with materials with high dielectric loss capacity and magnetic loss capacity; aiming at the problems of insufficient microwave absorption performance and the like of a single CNT wave-absorbing material. In view of the problems, the invention relates to a material structureTo begin with, it is proposed to use polystyrene microspheres as templates to alter CNT/TiO 2 The surface structure of the composite wave-absorbing material is adopted, so that the wave-absorbing performance of the material is improved.
(2) The preparation method adopts easily-obtained raw materials, can obtain a material with excellent electromagnetic wave absorption performance through simple preparation steps, has simple preparation process operation, is easy to implement, and is easy for industrial production.
Drawings
Fig. 1: (a) And (b) the SEM images of the material before and after firing in step (4) according to example 1 of the present invention, respectively.
Fig. 2: (c) And (d) the SEM images of the material before and after firing in step (4) according to example 2 of the present invention, respectively.
Fig. 3: (e) And (f) SEM images corresponding to the material before and after firing in step (4) according to example 3 of the present invention, respectively.
Fig. 4: (g) And (h) SEM images corresponding to the material of example 4 of the present invention before and after firing in step (4), respectively.
Fig. 5: SEM image of PS spheres prepared according to the examples of the present invention.
Fig. 6: honeycomb CNT/TiO prepared according to examples 1 to 4 of the present invention 2 XRD patterns of the composite wave-absorbing material prove that TiO 2 The particles are in the anatase crystal form.
FIGS. 7a, 7b, 7c and 7d are respectively the honeycomb CNTs/TiO prepared in examples 1-4 of the present invention 2 Reflection loss of the composite wave-absorbing material is schematically shown, wherein 7a corresponds to example 1,7b corresponds to example 2,7c corresponds to example 3, and 7d corresponds to example 4.
Detailed Description
Specific examples are given below to further illustrate the technical solution of the present invention, but it is worth illustrating: the following examples are not to be construed as limiting the scope of the invention, but as such, modifications and variations in the invention that are not essential to the invention will be apparent to those skilled in the art in light of the foregoing disclosure.
The CNT used in the examples of the present invention was manufactured by the scientific and technological company, carbon-rich graphene, su, outside diameter: 5-10nm, outside diameter: 10-20nm, length: 10-30 μm, which was prepared as a CNT dispersion with a concentration of 1mg/ml using absolute ethanol, was used in the following examples.
Examples used TiO 2 The preparation steps of (a) are as follows:
(1) Glacial acetic acid (7.67 mL) was added to the dry beaker (500 mL), followed by addition of butyl titanate (46.67 mL) thereto, and stirring electrically at room temperature for 15min;
(2) Deionized water (193.33 mL) was added to the beaker immediately with stirring, at which time a significant amount of white precipitate appeared immediately inside the beaker;
(3) Stirring for 1h continuously to completely hydrolyze the butyl titanate;
(4) Concentrated nitric acid (2.67 mL) (purity 65%) was then added to the dispersion;
(5) Heating the obtained mixed suspension to 78 ℃ at constant speed within 40min in a water bath box, and continuously preserving heat at 78 ℃ for 75min to obtain TiO 2 Precursor colloid;
(6) Then adding a small amount of deionized water into the mixture, and adjusting the volume of the colloid dispersion liquid to 270mL;
(7) Then transferring the dispersion liquid into a high-temperature titanium reaction kettle (4) with the volume of 80mL, heating to 240 ℃ and keeping for 12h;
(8) After cooling to room temperature, transferring to a 500mL beaker, adding concentrated nitric acid (1.6 mL) (purity 65%) to the dispersion, magnetically stirring for 10min, and ultrasonically cleaning for 10min;
(9) The precursor colloid obtained is respectively centrifugally separated and washed for 3 times by distilled water and absolute ethyl alcohol by a high-speed centrifugal machine at the rotating speed of 10000 rad/min;
(10) Dispersing in absolute ethyl alcohol to obtain nano-crystalline TiO with average grain diameter of 12nm 2 Colloid, its concentration was adjusted to 2mg/ml. The TiO 2 The crystalline phase of (a) is mainly of anatase structure.
The polystyrene microspheres used in the examples were prepared by the following method:
(1) Slowly add 3.75g PVPK30 to 212.5mL absolute ethanol, place in beaker A, add 0.375g AIBN to 37.5mL styrene, place in beaker B, and mix both in-beaker samples by magnetic stirring for 1 hour to complete mixing;
(2) Mixing the two materials, pouring into a 500mL round bottom flask, replacing a rubber plug, introducing argon, exhausting for 10min, and then placing into an oil bath pot at 73 ℃ for magnetic stirring for 24 hours;
(3) Centrifuging with absolute ethanol at 4000r/min for multiple times until no styrene smell exists, and dispersing into absolute ethanol to obtain polystyrene microsphere dispersion with concentration of 2mg/ml.
FIG. 5 shows a characterization diagram of PS (polystyrene) microspheres prepared by the invention, which can prove that the PS microspheres are uniform and have better morphology.
Example 1
Honeycomb CNT/TiO 2 The preparation method of the composite wave-absorbing material comprises the following steps:
(1) Taking 3ml of Polystyrene (PS) microsphere dispersion liquid with the concentration of 2mg/ml and TiO with the concentration of 2mg/ml 2 5ml of dispersion liquid and 3ml of CNT dispersion liquid with the concentration of 1mg/ml are mixed together and ultrasonic for 45min;
(2) Suction-filtering Polystyrene (PS) microsphere dispersion liquid and TiO by using suction filter 2 Forming a film by the dispersion liquid and the mixed liquid of the CNT and the absolute ethyl alcohol;
(3) Transferring the sample film after suction filtration into a blast drying oven for ordinary drying at 70 ℃ for 10 hours;
(4) Heating to 500 ℃ in Ar atmosphere by using a vacuum tube furnace at a heating rate of 10 ℃/min, and preserving heat for 2 hours to obtain the honeycomb CNT/TiO 2 Composite wave-absorbing material.
Fig. 1 (a) and (b) correspond to SEM images of the material of example 1 of the present invention before and after firing in step (4), respectively; the figure shows that the PS spheres are small in quantity and form a honeycomb structure, and the honeycomb structure prepared by the mixed solution of the CNT and the absolute ethyl alcohol with the content is general in effect.
Honeycomb CNT/TiO prepared in example 1 2 XRD patterns of the composite wave-absorbing material are shown in FIG. 6, and TiO is shown 2 The particles are in the anatase crystal form.
Honeycomb CNT/TiO prepared in example 1 2 Test experiments of the performance of the composite wave-absorbing material are as followsThe following is implemented:
the invention adopts a vector network analyzer as test equipment and measures corresponding electromagnetic parameters by adopting a coaxial method. The system to be tested is calibrated first, and then the sample is tested, so that the corresponding electromagnetic parameters of the sample are determined. The coaxial method is adopted for testing, and the sample is subjected to compression ring treatment first. The compression ring adopts a customized compression ring die, the total mass is 0.05g, and the samples are mixed and melted according to the mass ratio, namely, paraffin=15:85, and the compression ring is formed. The thickness of the final coaxial test sample is between 1mm and 4 mm.
Honeycomb CNT/TiO prepared in example 1 2 The reflection loss of the composite absorbing material is schematically shown in fig. 7a, and it can be seen that the absorbing material of example 1 has good absorbing performance. This shows that the attenuation of the incident electromagnetic wave due to the CNT/TiO is increased due to the honeycomb structure 2 Is reduced by polarization loss and is trapped in the honeycomb structure, in the CNT/TiO 2 Multiple reflections are carried out between the composite walls, and finally good wave absorbing performance can be achieved.
Example 2
Honeycomb CNT/TiO 2 The preparation method of the composite wave-absorbing material comprises the following steps:
(1) Taking 3ml of Polystyrene (PS) microsphere dispersion liquid with the concentration of 2mg/ml and TiO with the concentration of 2mg/ml 2 5ml of dispersion liquid and 5ml of CNT dispersion liquid with the concentration of 1mg/ml are mixed together and ultrasonic treated for 45min;
(2) Suction-filtering Polystyrene (PS) microsphere dispersion liquid and TiO by using suction filter 2 Forming a film by the dispersion liquid and the mixed liquid of the CNT and the absolute ethyl alcohol;
(3) Transferring the sample film after suction filtration into a blast drying oven for ordinary drying at 70 ℃ for 10 hours;
(4) Heating to 500 ℃ in Ar atmosphere by using a vacuum tube furnace at a heating rate of 10 ℃/min, and preserving heat for 2 hours to obtain the honeycomb CNT/TiO 2 Composite wave-absorbing material.
Example 2 differs from example 1 in that: in the step (1), the adding volume of the CNT dispersion liquid with the concentration of 1mg/ml is changed from 3ml to 5ml; otherwise, the same as in example 1 was conducted.
Fig. 2 (c) and (d) correspond to SEM images of the material of example 2 before and after firing in step (4), respectively, showing that the PS spheres were large and uniform in amount and the honeycomb structure was formed, and that the honeycomb structure prepared with the CNT and absolute ethanol mixed solution of this content was excellent.
Honeycomb CNT/TiO prepared according to example 2 of the present invention 2 XRD patterns of the composite wave-absorbing material are shown in figure 6, which proves that TiO 2 The particles are in the anatase crystal form.
Example 2 preparation of honeycomb CNT/TiO 2 Test of Performance of composite wave absorbing Material referring to example 1, honeycomb CNT/TiO prepared in example 2 of the present invention 2 The reflection loss of the composite absorbing material is schematically shown in fig. 7b, which demonstrates that the absorbing material of example 2 has good absorbing properties.
Example 3
Honeycomb CNT/TiO 2 The preparation method of the composite wave-absorbing material comprises the following steps:
(1) Taking 3ml of Polystyrene (PS) microsphere dispersion liquid with the concentration of 2mg/ml and TiO with the concentration of 2mg/ml 2 5ml of dispersion liquid and 8ml of CNT dispersion liquid with the concentration of 1mg/ml are mixed together and ultrasonic for 45min;
(2) Suction-filtering Polystyrene (PS) microsphere dispersion liquid and TiO by using suction filter 2 Forming a film by the dispersion liquid and the mixed liquid of the CNT and the absolute ethyl alcohol;
(3) Transferring the sample film after suction filtration into a blast drying oven for ordinary drying at 70 ℃ for 10 hours;
(4) Heating to 500 ℃ in Ar atmosphere by using a vacuum tube furnace at a heating rate of 10 ℃/min, and preserving heat for 2 hours to obtain the honeycomb CNT/TiO 2 Composite wave-absorbing material.
Example 3 differs from example 1 in that: in the step (1), the adding volume of the CNT dispersion liquid with the concentration of 1mg/ml is changed from 3ml to 8ml; otherwise, the same as in example 1 was conducted.
Fig. 3 (e) and (f) correspond to SEM images of the material of example 3 before and after firing in step (4), respectively, in which PS spheres were large and uniform in amount and a honeycomb structure was formed, and it was confirmed that the honeycomb structure prepared with the CNT and absolute ethanol mixed solution of this content was excellent.
Honeycomb CNT/TiO prepared according to example 3 of the present invention 2 XRD patterns of the composite wave-absorbing material are shown in figure 6, which proves that TiO 2 The particles are in the anatase crystal form.
Honeycomb CNT/TiO prepared according to example 3 of the present invention 2 Test of Performance of composite absorbing Material referring to example 1, example 3 prepared honeycomb CNT/TiO 2 The reflection loss of the composite wave-absorbing material is schematically shown in fig. 7c, which demonstrates that the wave-absorbing material prepared in example 3 is excellent in wave-absorbing performance.
Example 4
Honeycomb CNT/TiO 2 The preparation method of the composite wave-absorbing material comprises the following steps:
(1) Taking 3ml of Polystyrene (PS) microsphere dispersion liquid with the concentration of 2mg/ml and TiO with the concentration of 2mg/ml 2 5ml of dispersion liquid and 10ml of CNT dispersion liquid with the concentration of 1mg/ml are mixed together and ultrasonic for 45min;
(2) Suction-filtering Polystyrene (PS) microsphere dispersion liquid and TiO by using suction filter 2 Forming a film by the dispersion liquid and the mixed liquid of the CNT and the absolute ethyl alcohol;
(3) Transferring the sample film after suction filtration into a blast drying oven for ordinary drying at 70 ℃ for 10 hours;
(4) Heating to 500 ℃ in Ar atmosphere by using a vacuum tube furnace at a heating rate of 10 ℃/min, and preserving heat for 2 hours to obtain the honeycomb CNT/TiO 2 Composite wave-absorbing material.
Example 4 differs from example 1 in that: in the step (1), the adding volume of the CNT dispersion liquid with the concentration of 1mg/ml is changed from 3ml to 10ml; otherwise, the same as in example 1 was conducted.
The graphs (g) and (h) of fig. 4 correspond to SEM images of the material of example 4 before and after firing in step (4), respectively, in which the PS spheres are large and uniform and the honeycomb structure is formed, and it is proved that the honeycomb structure prepared by using the CNT and absolute ethanol mixed solution with the content is good.
Honeycomb CNT/TiO prepared according to example 4 of the present invention 2 XRD patterns of the composite wave-absorbing material are shown in figure 6, which proves that TiO 2 The particles are in the anatase crystal form.
Honeycomb CNT/TiO prepared according to example 4 of the present invention 2 Test of Performance of composite absorbing Material referring to example 1, honeycomb CNT/TiO prepared in example 4 2 The reflection loss of the composite wave-absorbing material is schematically shown in fig. 7d, which demonstrates that the wave-absorbing material prepared in example 4 is excellent in wave-absorbing performance.
Honeycomb CNT/TiO prepared in comparative example 4 2 As can be seen from the wave absorbing performance of the composite wave absorbing material, the Polystyrene (PS) microsphere is more fully arranged on the CNT/TiO as the mass fraction of the CNT is increased 2 The composite material leaves more honeycomb structures, the honeycomb structure is firmer, and the absorption of the incident electromagnetic wave is enhanced. The excellent electromagnetic shielding effect is a synergistic effect of conductivity and repeated reflection.

Claims (10)

1. Honeycomb CNT/TiO 2 The preparation method of the composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1: tiO with the concentration of 1-4 mg/ml is prepared by using absolute ethyl alcohol as dispersing agent 2 A dispersion, a CNT dispersion having a concentration of (1-4) mg/ml, and a polystyrene microsphere dispersion having a concentration of (1-4) mg/ml; dispersing the polystyrene microsphere dispersion liquid and TiO 2 Mixing the dispersion liquid and the CNT dispersion liquid according to the volume ratio of 3-5:3-5:3-10, and performing ultrasonic treatment to obtain a mixed dispersion liquid;
step 2: filtering the mixed dispersion liquid by a suction filter to form a film;
step 3: transferring the sample film obtained in the step (2) after suction filtration into a blast drying box for drying;
step 4: heating the dried sample film obtained in the step 3 to 400-550 ℃ at a heating rate of 5-10 ℃/min in Ar atmosphere by using a vacuum tube furnace, and preserving heat for 1-3 hours to obtain the honeycomb CNT/TiO 2 A composite material.
2. The method of manufacturing according to claim 1, wherein: the TiO 2 Is nano-scale TiO 2 The average grain size is between 10nm and 30nm, and the crystal phase is mainly in anatase structure.
3. The method of manufacturing according to claim 1, wherein: the polystyrene microsphere is uniform in size and has an average sphere diameter of 0.2-3 mu m.
4. The method of manufacturing according to claim 1, wherein: in step 1, tiO 2 The concentration of the dispersion was 2mg/ml, the concentration of the CNT dispersion was 1mg/ml, and the concentration of the polystyrene microsphere dispersion was 2mg/ml.
5. The method of claim 1 or 4, wherein: polystyrene microsphere dispersion and TiO 2 The mixing volume ratio of the dispersion liquid and the CNT dispersion liquid is 3:5:3-10.
6. The method of manufacturing according to claim 5, wherein: polystyrene microsphere dispersion and TiO 2 The mixing volume ratio of the dispersion liquid and the CNT dispersion liquid is 3:5:8-10.
7. The method of manufacturing according to claim 1, wherein: in the step 3, the working temperature of the blast drying box is 50-70 ℃ and the drying time is 6-10 h.
8. The method of manufacturing according to claim 1, wherein: in step 4, a vacuum tube furnace is used, and the temperature is raised to 500 ℃ and kept for 2 hours in an Ar gas atmosphere at a heating rate of 10 ℃/min.
9. A honeycomb CNT/TiO film prepared by the method of claim 1 2 A composite material.
10. The honeycomb CNT/TiO according to claim 9 2 The application of the composite material as an electromagnetic wave absorbing material.
CN202310181627.0A 2023-02-23 2023-02-23 Honeycomb CNT/TiO 2 Composite material, preparation method and application thereof Pending CN116332162A (en)

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