CN113088075B - Chiral planar spiral PPy/Fe3O4Composite broadband microwave absorbent and preparation method and application thereof - Google Patents
Chiral planar spiral PPy/Fe3O4Composite broadband microwave absorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of microwave absorption and discloses chiral planar spiral PPy/Fe3O4A composite broadband microwave absorbent, a preparation method and application thereof. The invention takes a surfactant as a soft template and adopts a chemical oxidative polymerization reaction method to prepare the planar spiral polypyrrole with unique appearance, and the diameter of the planar spiral polypyrrole is 20-40 mu m. The material is used as a precursor, and the material and ferric salt and other raw materials are prepared into chiral polypyrrole and Fe through a dissolution thermal method3O4The compound not only has novel and unique appearance, but also can regulate and control Fe by changing the concentration of iron ions in a system and the volume of added deionized water3O4The content and the size of the growth on the surface of the polypyrrole, and the polypyrrole has excellent microwave absorption characteristics. The controllable preparation process disclosed by the invention is simple and the product has novel appearance, overcomes the defects of harsh reaction conditions, difficult regulation and control of the appearance of the reaction product, poor experimental repeatability and the like in the conventional preparation process, and has good industrial application potential.
Description
Technical Field
The invention belongs to the field of microwave absorption, and particularly relates to chiral planar spiral PPy/Fe3O4A composite broadband microwave absorbent, a preparation method and application thereof.
Background
The chiral conductive polymer has high conductivity of pi-pi conjugated polymer chains and similar metals, good processability, easily-tuned band gaps and rich electric activity, and is widely researched in the fields of chiral sensors, supercapacitors and the like. In addition, the composite material has the unique advantages of good environmental stability, low cost, low density, adjustable conductivity, larger frequency conversion absorption range and the like, and has great application potential in the field of electromagnetic wave absorption.
The shape of the high-performance electromagnetic wave-absorbing material is another important factor for determining the performance of the high-performance electromagnetic wave-absorbing material. The morphology of the common chiral polymers at present mainly comprises: spiral, fiber, ribbon, sphere, etc. Chinese patent document (CN108729027B) discloses a chiral polyaniline fiber wave-absorbing system and a preparation method thereof, wherein the synthesis of a chiral polymer is realized by adding chiral doping acid, but the reagent is toxic and the appearance is difficult to regulate and control; chinese patent document (CN110964142B) discloses a preparation method of chiral polymer microspheres with a porous structure, which has dispersed and uniform appearance, complex and complicated operation and poor experimental repeatability; chinese patent document (CN109280118A) discloses a mono-chiral helical polymer of poly-9, 9-dipropynyl fluorene skeleton structure with high stereoregularity and its preparation method, which is complex to operate and has low yield. In addition, the chiral structure is successfully prepared by adding chiral additives and some toxic and odorous organic reagents, the appearance of the chiral structure is mostly in structures such as a three-dimensional helix, a one-dimensional rod shape, a zero-dimensional particle and the like, and a two-dimensional plane chiral structure is not reported.
With the rapid development of 5G mobile networks, the development of high-performance electromagnetic wave absorbing structures/wave absorbers is urgently needed to solve the problem of increasingly serious electromagnetic interference. Among various candidate materials, the composite wave-absorbing material formed by combining the chiral structure with the material serving as the wave-absorbing agent has wide application prospect in the wave-absorbing field due to unique geometric configuration and excellent performance. However, the shape and size of the existing composite wave-absorbing material are difficult to regulate, the experimental steps are complicated, the conditions are harsh, the operation is complex, the experimental repeatability is poor, and in addition, the wave-absorbing performance of the composite wave-absorbing material is difficult to meet the requirements of thinness, lightness, width and strength.
Therefore, the problem to be solved by those skilled in the art is how to develop a chiral polymer material with a better microwave absorption property, which has a simple and convenient process, is easy to industrialize, and has a controllable morphology and a controllable size.
Disclosure of Invention
In view of this, the present invention provides a composite broadband microwave absorbent with simple process and controllable size.
In order to achieve the purpose, the invention adopts the following technical scheme:
chiral planar spiral PPy/Fe3O4Composite broadband microwave absorbent comprising polypyrrole with planar helical structure and Fe with uniform particle size3O4Nanoparticles, and said Fe3O4The nano particles grow on the surface of the planar spiral polypyrrole, wherein the atomic ratio of Fe to C is 1 (6.78-11.62).
It is worth to say that in order to realize the regulation and control of the characteristics of the wave absorbing agent such as conductivity, electromagnetic property, wave absorbing property and the like, in the invention, Fe3O4The mass ratio of the polypyrrole to the polypyrrole is 1 (7-9).
Furthermore, the diameter of the planar spiral polypyrrole is 20-40 mu m, and Fe3O4The particle size of the nano particles is 15-20 nm; and the number of the first and second electrodes,
the PPy structure is a planar spiral sheet formed by winding a single-chain ultra-long nano chain along the center.
The chiral composite broadband microwave absorbent disclosed by the invention has excellent microwave absorption characteristics, wherein the maximum effective bandwidth of the reflectivity less than or equal to-10 dB is 4.72-10.08 GHz, and the maximum absorption is-37.50-47.93 dB.
The second purpose of the invention is to provide a preparation method of the chiral composite broadband microwave absorbent.
In order to achieve the above purpose, the invention provides the following technical scheme:
the preparation method of the eutectic compound with solid-state fluorescence property comprises the following steps:
(1) weighing a certain mass of surfactant, dissolving the surfactant in a certain volume of deionized water, and stirring for 10-15 min at 30-50 ℃; crystallizing in ice bath for 60-90 min to obtain a crystal suspension of the surfactant;
(2) adding an oxidant and a pyrrole monomer into the crystallization suspension, and performing oxidative polymerization to obtain a crude product PPy;
(3) carrying out centrifugal washing and vacuum freeze drying on the crude product PPy for multiple times to obtain the planar spiral polypyrrole precursor;
(4) adding the precursor, ferric salt, surfactant, water and reducing agent into a glycol solution according to a certain proportion, and stirring to obtain a uniformly mixed solution;
(5) transferring the solution into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into an oven, and carrying out high-temperature reaction to obtain a crude product PPy/Fe3O4；
(6) Mixing the crude product PPy/Fe3O4And finally obtaining the chiral composite broadband microwave absorbent through multiple times of centrifugal washing and vacuum freeze drying.
It is worth to say that the invention adopts chemical oxidative polymerization and dissolution thermal method to prepare the planar spiral polypyrrole and the planar spiral polypyrrole has Fe grown on the surface3O4Compared with the existing method, the chiral composite broadband microwave absorbent obtained by the invention has a two-dimensional plane chiral structure, is greatly innovative in appearance, and has the advantages of high experimental repeatability, simple steps and low requirement on instrument precision.
Further, the surfactant in the step (1) is Cetyl Trimethyl Ammonium Bromide (CTAB), and the concentration of the surfactant is 4.3-20 mmol/L; or the like, or, alternatively,
the surfactant in the step (1) is a mixture of Cetyl Trimethyl Ammonium Bromide (CTAB), polyacrylic acid (PAA) and polyethylene glycol (PEG), and the proportion of the mixture is 1 (1-3).
Further, the oxidant in the step (2) is ammonium persulfate, and the concentration ratio of the ammonium persulfate to the pyrrole monomer is 1 (2-4).
Further, the centrifugal speed of centrifugal washing in the steps (3) and (6) is 4000rpm, and the centrifugal time is 3-5 min; and the number of the first and second electrodes,
the vacuum freeze-drying temperature is-60 ℃.
Further, the concentration of the ferric salt in the step (4) is 0.064-0.128 mol/L, the surfactant is polyacrylic acid, and the alkali is sodium acetate; the volume fraction of polyacrylic acid and the concentration of sodium acetate are respectively 0.34-0.40% and 0.36-0.42 mol/L; the volume ratio of the water to the glycol is 1 (2-5).
Further, in the step (5), the high-temperature reaction time is 12 hours, and the reaction temperature is 180-200 ℃.
It is worth to be noted that the planar spiral polypyrrole prepared by the chemical oxidative polymerization and the dissolution thermal method of the invention grows Fe on the surface3O4The particle compound has novel appearance, and Fe can be regulated and controlled by changing the concentration of ferric salt in the system and the volume of added deionized water3O4Content and size of (c); various morphologies such as flat flights, monodisperse hexagonal flights, irregularly-intercalated multi-flights or flights of larger size are prepared by adding different surfactant types.
The third purpose of the invention is to provide the application of the chiral composite broadband microwave absorbent in the microwave absorption field.
In order to achieve the above purpose, the invention provides the following technical scheme:
the chiral plane spiral PPy/Fe3O4The composite broadband microwave absorbent is applied to the preparation of nano electronic equipment, sensors, supercapacitors, photocatalysis or lithium ion batteries.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention takes the surfactant as a soft template and adopts chemical oxidationThe polymerization reaction method prepares the planar spiral polypyrrole with unique appearance, and the diameter of the planar spiral polypyrrole is 20-40 mu m. The material is used as a precursor, and is prepared into chiral polypyrrole and Fe with ferric salt and other raw materials by a dissolution thermal method3O4The compound not only has novel and unique appearance, but also can regulate and control Fe by changing the concentration of iron ions in a system and the volume of added deionized water3O4The content and size of the growth on the surface of the polypyrrole have excellent microwave absorption characteristics;
2. the invention discloses a planar spiral polypyrrole surface growth Fe3O4The particle compound is prepared by chemical oxidative polymerization and a dissolution thermal method, so that the particle compound has the advantages of simple and convenient process, good repeatability and large-scale production; the compound prepared by the method has the excellent characteristics of novel structure, good dispersity and uniformity, adjustable size and the like;
3. the invention discloses chiral polypyrrole such as the planar spiral slice, the monodisperse hexagonal spiral slice, the multi-spiral slice mixed with irregularity, the spiral slice with larger size and the like, and Fe grown on the surface of the planar spiral polypyrrole3O4The preparation method of the particles is convenient to operate, green and environment-friendly, has low requirement on instrument precision, and has good industrial application potential.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts
Fig. 1 to 2 show the phase and morphology of the product obtained in example 1 of the present invention under XRD and scanning electron microscope, respectively.
FIG. 3 is a reflectance curve at a mass fraction of 25% for the product obtained in example 1 of the present invention.
FIGS. 4 to 8 show the phase, composition, electromagnetic properties and morphology of the product obtained in example 2 of the present invention measured by XRD, FTIR, VSM and scanning electron microscopy.
FIG. 9 is a reflectance curve of 25% by mass of a product obtained in example 2 of the present invention.
FIGS. 10 to 12 show the phases and morphologies of the product obtained in example 3 of the present invention measured by XRD and scanning electron microscopy.
Fig. 13 to 15 show the phases and the morphologies of the product obtained in example 4 of the present invention measured by XRD and scanning electron microscopy.
FIG. 16 shows the morphology of the product obtained in example 5 of the present invention measured under a scanning electron microscope.
FIG. 17 shows the morphology of the product obtained in example 6 of the present invention measured under a scanning electron microscope.
FIGS. 18 to 19 are the shapes of the products obtained in example 7 of the present invention measured under a scanning electron microscope.
FIGS. 20 to 21 are graphs of the products obtained in example 8 of the present invention measured under a scanning electron microscope.
FIGS. 22 to 23 show the shapes of the products obtained in example 9 of the present invention under a scanning electron microscope.
FIG. 24 shows the morphology of the product obtained in example 10 of the present invention measured under a scanning electron microscope.
FIG. 25 shows the morphology of the product obtained in example 11 under a scanning electron microscope.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
Example 1
A polypyrrole with a planar spiral structure and a preparation method thereof specifically comprise the following steps:
0.5465g C will be mixed19H42BrN (CTAB) dissolved in 150mL deionized water, and magnetically stirred for 10min at 40 ℃ to form colorless solution; then placing the solution in an ice bath condition, and standing for 1h to crystallize; 1.027g (NH)4)2S2O8(APS) dissolved in 25mL deionized water was added to the solution in one portion, after 10s interval, 0.5mL C was added4H5And N (py), stirring for 10min to uniformly mix the solution, standing at 0-3 ℃ for 24h, alternately washing with absolute ethyl alcohol and deionized water, and drying in a vacuum freeze drying oven at-60 ℃ to finally obtain the polypyrrole with the planar spiral structure.
The phases and the appearances of the obtained products measured under XRD and scanning electron microscope are respectively shown in figures 1-2. From the above analysis, the product is single-chain ultra-long nano-chain, and is wound into a planar spiral sheet along the center.
The heterogeneous material was filled in a base material at a mass fraction of 25%, and the measured reflectance was as shown in FIG. 3, in which the effective bandwidth of the-10 dB or less reflectance was 5.84GHz and the maximum reflection loss was-48.17 dB.
Example 2
Chiral plane spiral PPy/Fe3O4The composite broadband microwave absorbent, the preparation method thereof and the composite wave-absorbing material containing the absorbent comprise the following specific steps:
1.35g FeCl3·6H2O, 12mL of deionized water, 0.19mL of PAA, 0.5g of the PPy precursor prepared in the example 1 is added into 40mL of ethylene glycol solution, the mixture is magnetically stirred for 30min, 1.6406g of NaAc is added, the mixture is continuously stirred for 2h, then the solution is transferred into a polytetrafluoroethylene lining, the polytetrafluoroethylene lining is placed into a high-temperature oven to react for 12h at the high temperature of 200 ℃, the mixture is naturally cooled to the room temperature, the absolute ethyl alcohol and the deionized water are alternately used for washing, the mixture is dried in a vacuum freeze drying oven at the temperature of 60 ℃ below zero, and finally Fe growing on the surface of the planar spiral polypyrrole is obtained3O4A composite of particles.
The phase, composition, electromagnetic property and morphology of the obtained product measured under XRD, FTIR, VSM and scanning electron microscope are respectively shown in figures 4-8. From the above analysis, the product was a planar helical polypyrrole coated with uniform and monodisperse ferroferric oxide particles. Wherein the diameter of the spiral polypyrrole is about 30 μm, and the particle size of the ferroferric oxide is about 15-20 nm. Wherein the atomic percentages of Fe and C are 1: 8.8.
the heterogeneous material was filled in a base material at a mass fraction of 25%, and the measured reflectance was as shown in fig. 9, in which the effective bandwidth of-10 dB reflectance or less was 8.88GHz, and the maximum reflection loss was-44.75 dB.
Example 3
Chiral plane spiral PPy/Fe3O4Compared with the preparation steps disclosed in example 2, the only difference of the composite broadband microwave absorbent and the preparation method thereof is that: fe3+The concentration of (A) is 0.128M, and the other preparation steps and process parameters are the same.
The phases and the appearances of the obtained products measured under XRD and scanning electron microscope are respectively shown in figures 10-12. Wherein the atomic percentages of Fe and C are 1: 6.9.
analysis shows that the content of the ferroferric oxide particles coated on the surface of the product is obviously higher than that of the ferroferric oxide particles coated on the surface of the product in example 2.
Example 4
Chiral plane spiral PPy/Fe3O4Compared with the preparation steps disclosed in example 2, the only difference of the composite broadband microwave absorbent and the preparation method thereof is that: fe3+The concentration of (A) is 0.064M, and the other preparation steps and process parameters are the same.
The phases and the appearances of the obtained products measured under XRD and scanning electron microscope are respectively shown in figures 13-15. Wherein the atomic percentages of Fe and C are 1: 10.74.
analysis shows that the content of the ferroferric oxide particles coated on the surface of the product is obviously less than that of the ferroferric oxide particles in example 2.
Example 5
Chiral plane spiral PPy/Fe3O4Composite broadband microwave absorbent, preparation method and implementation thereofThe only difference compared to the preparation steps disclosed in example 2 is that: the volume of water added in the reaction is 15mL, and the rest preparation steps and technological parameters are the same.
The morphology of the obtained product measured under a scanning electron microscope is shown in fig. 16. Analysis shows that the ferroferric oxide particles coated on the surface of the product are smaller than those in the example 2. Wherein the particle size of the ferroferric oxide particles is about 10-20 nm. Wherein the atomic percentages of Fe and C are 1: 11.62.
example 6
Chiral plane spiral PPy/Fe3O4Compared with the preparation steps disclosed in example 2, the only difference of the composite broadband microwave absorbent and the preparation method thereof is that: the volume of water added for the reaction was 7.5mL, and the remaining preparation steps and process parameters were the same.
The appearance of the obtained product measured under a scanning electron microscope is shown in fig. 17. Analysis shows that the ferroferric oxide particles coated on the surface of the product are larger than those in the example 2. Wherein the particle size of the ferroferric oxide particles is about 100-150 nm. Wherein the atomic percentages of Fe and C are 1: 6.78.
example 7
Chiral plane spiral PPy/Fe3O4Compared with the preparation steps disclosed in example 1, the only difference of the composite broadband microwave absorbent and the preparation method thereof is that: CTAB is added into deionized water, 0.2g of PAA is added at the same time, and the other preparation steps and process parameters are the same.
The appearance of the obtained product measured under a scanning electron microscope is shown in FIGS. 18-19. Analysis revealed that the product was a uniform and dispersed hexagonal spiral. Wherein the long axis of the hexagonal spiral sheet is about 8-12 μm, and the short axis is about 4-7 μm.
Example 8
Chiral plane spiral PPy/Fe3O4Compared with the preparation steps disclosed in example 1, the only difference of the composite broadband microwave absorbent and the preparation method thereof is that: CTAB is added into deionized water, 0.2g of PEG is added at the same time, and other preparation steps and process parameters are the same.
The appearance of the obtained product measured under a scanning electron microscope is shown in figures 20-21. Analysis shows that the product is a dispersed irregular spiral sheet, wherein the diameter of the spiral polypyrrole is about 10-15 μm.
Example 9
Chiral plane spiral PPy/Fe3O4Compared with the preparation steps disclosed in example 1, the only difference of the composite broadband microwave absorbent and the preparation method thereof is that: CTAB is added into deionized water, 0.1g of glutamic acid is added at the same time, and other preparation steps and process parameters are the same.
The appearance of the obtained product measured under a scanning electron microscope is shown in FIGS. 22-23. Analysis shows that the product is a dispersed helical sheet with larger size, wherein the diameter of the helical polypyrrole is about 20-35 μm.
Example 10
Chiral plane spiral PPy/Fe3O4Compared with the preparation steps disclosed in example 1, the only difference of the composite broadband microwave absorbent and the preparation method thereof is that: the mass of CTAB added in the reaction is 0.273g, and the rest preparation steps and process parameters are the same.
The shapes of the obtained products measured under a scanning electron microscope are respectively shown in FIG. 24. Analysis shows that the product is multi-helical sheet with irregular inclusion.
Example 11
Chiral plane spiral PPy/Fe3O4Compared with the preparation steps disclosed in example 1, the only difference of the composite broadband microwave absorbent and the preparation method thereof is that: the mass of CTAB added in the reaction is 1.093g, and the rest preparation steps and technological parameters are the same.
The shapes of the obtained products measured under a scanning electron microscope are respectively shown in FIG. 25. Analysis shows that the product is a polypyrrole spiral sheet with larger size, wherein the diameter of the spiral polypyrrole is about 60-300 μm.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The method disclosed in the embodiment corresponds to the method disclosed in the embodiment, so that the description is simple, and the relevant points can be referred to the description of the method part.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. Chiral planar spiral PPy/Fe3O4The composite broadband microwave absorbent is characterized by comprising polypyrrole PPy with a planar spiral structure and Fe with uniform particle size3O4Nanoparticles, and said Fe3O4The nano particles grow on the surface of the planar spiral polypyrrole, wherein the atomic ratio of Fe to C is 1 (6.78-11.62); the diameter of the polypyrrole PPy is 20-40 mu m, and Fe3O4The particle size of the nano particles is 15-20 nm; the polypyrrole PPy structure is a planar spiral sheet formed by winding a single-chain ultra-long nano chain along the center;
the chiral plane spiral PPy/Fe3O4The preparation method of the composite broadband microwave absorbent comprises the following steps:
(1) weighing a certain mass of surfactant, dissolving the surfactant in a certain volume of deionized water, and stirring for 10-15 min at 30-50 ℃; crystallizing in ice bath for 60-90 min to obtain a crystal suspension of the surfactant;
(2) adding an oxidant and a pyrrole monomer into the crystallization suspension, and performing oxidative polymerization to obtain a crude product PPy;
(3) carrying out centrifugal washing and vacuum freeze drying on the crude product PPy for multiple times to obtain a planar spiral polypyrrole precursor;
(4) adding the precursor, ferric salt, surfactant, water and alkali into a glycol solution according to a certain proportion, and stirring to obtain a uniformly mixed solution;
(5) transferring the solution into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into an oven, and carrying out high-temperature reaction to obtain a crude product PPy/Fe3O4；
(6) Mixing the crude product PPy/Fe3O4The chiral plane spiral PPy/Fe is finally obtained after multiple times of centrifugal washing and vacuum freeze drying3O4Composite broadband microwave absorbent;
wherein the surfactant in the step (1) is Cetyl Trimethyl Ammonium Bromide (CTAB), and the concentration of the surfactant is 4.3-20 mmol/L;
the surfactant in the step (4) is polyacrylic acid.
2. The chiral planar helical PPy/Fe of claim 13O4The composite broadband microwave absorbent is characterized in that the oxidant in the step (2) is ammonium persulfate, and the concentration ratio of the ammonium persulfate to the pyrrole monomer is 1 (2-4).
3. The chiral planar helical PPy/Fe of claim 13O4The composite broadband microwave absorbent is characterized in that the centrifugal speed of centrifugal washing in the steps (3) and (6) is 4000rpm, and the centrifugal time is 3-5 min; and the vacuum freeze-drying temperature is-60 ℃.
4. The chiral planar helical PPy/Fe of claim 13O4The composite broadband microwave absorbent is characterized in that in the step (4), the concentration of ferric salt is 0.064-0.128 mol/L, the surfactant is polyacrylic acid, and the alkali is sodium acetate; the volume fraction of polyacrylic acid and the concentration of sodium acetate are respectively 0.34-0.40% and 0.36-0.42 mol/L; the volume ratio of the water to the glycol is 1 (2-5).
5. The chiral planar helical PPy/Fe of claim 13O4The composite broadband microwave absorbent is characterized in that in the step (5), the high-temperature reaction time is 12 hours, and the reaction temperature is 180-200 ℃.
6. The chiral planar helical PPy/Fe of claim 13O4The application of the composite broadband microwave absorbent in the microwave absorption field is characterized in that the chiral plane helical PPy/Fe3O4The composite broadband microwave absorbent is applied to the preparation of nano electronic equipment, sensors, supercapacitors, photocatalysis or lithium ion batteries.
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