CN113527721A - Preparation method of broadband adjustable wave-absorbing hydrogel - Google Patents

Preparation method of broadband adjustable wave-absorbing hydrogel Download PDF

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CN113527721A
CN113527721A CN202110923808.7A CN202110923808A CN113527721A CN 113527721 A CN113527721 A CN 113527721A CN 202110923808 A CN202110923808 A CN 202110923808A CN 113527721 A CN113527721 A CN 113527721A
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刘宇
傅雅琴
齐晓明
钱晨
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Zhejiang Sci Tech University ZSTU
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Abstract

The invention provides a broadband antennaWave-modulating hydrogel and a preparation method thereof. The invention is formed by self-assembling Ti3C2TxMXene and polyacrylamide hydrogel are compounded to prepare the broadband adjustable electromagnetic wave absorption hydrogel. Through polyacrylamide hydrogel network and self-assembled Ti3C2TxMXene compounding is adopted to enhance the electromagnetic wave absorption intensity and bandwidth of the composite hydrogel material; in addition, the water content of the hydrogel is controlled by adjusting the proportion of water and glycerol in the liquid phase, so that the electromagnetic wave absorption frequency band and the absorption strength of the composite hydrogel are changed. The wave-absorbing hydrogel disclosed by the invention is high in wave-absorbing strength, wide in wave-absorbing bandwidth, good in wave-absorbing effect and simple in preparation process, and can be used for industrial production.

Description

Preparation method of broadband adjustable wave-absorbing hydrogel
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a preparation method of broadband adjustable wave-absorbing hydrogel.
Background
As is well known, electromagnetic wave absorbing materials have great application requirements in both the military stealth technology field and the civil electromagnetic wave prevention and control field. Particularly, with the rapid development of communication technology, the expectation of novel wave-absorbing materials which can meet the requirements of different occasions and are made of the same material is higher and higher.
The water-based wave-absorbing material is prepared from the novel wave-absorbing material by utilizing the high dielectric constant of water and the strong loss characteristic of electromagnetic waves. But has the problems of easy water loss, low wave-absorbing frequency band, unsatisfactory wave-absorbing effect and the like.
The hydrogel is a water-soluble functional polymer water-absorbing and water-storing material formed by the combined action of covalent bonds, hydrogen bonds, van der waals force and other acting forces. The polyacrylamide hydrogel has strong water storage capacity due to the fact that the side chain contains a large number of amide groups, has the advantages of being non-toxic, easy to recover, degradable and the like, and is an ideal water storage material.
However, most of the electromagnetic waves are reflected by water due to poor impedance matching between water and air, so that a single hydrogel material is difficult to achieve broadband and efficient absorption of the electromagnetic waves, and water in the hydrogel risks being lost during climate change.
Disclosure of Invention
Aiming at the problems and technical defects in the prior art, the invention provides a broadband adjustable composite wave-absorbing hydrogel and a preparation method thereof.
The adopted scheme is as follows:
the broadband adjustable composite wave-absorbing hydrogel is made of self-assembled Ti3C2TxMXene and polyacrylAmine hydrogel, wherein the self-assembly type Ti3C2TxThe content of MXene is 1-30 wt%, and the water content of the hydrogel is 20-40 vol%. The self-assembled Ti3C2TxPolypyrrole nanowire (PPyNWs-Cl) doped with chloride ion by MXene and Ti3C2TxMXene is formed by self-assembly in water. Wherein PPyNWs-Cl has negative charge, Ti3C2TxMXene has a positive charge; the two are mutually adsorbed by the action of electrostatic force, and PPyNWs-Cl is inserted in the middle of the MXene sheet layer to form an electrostatic self-assembly structure.
Further, the polypyrrole nanowire doped with chloride ions is generated by polymerizing a pyrrole monomer dissolved in 0.2M dilute hydrochloric acid and hexadecyl trimethyl ammonium bromide in an ice bath through an initiator, wherein the hexadecyl trimethyl ammonium bromide is used as a soft template, the molar ratio of the hexadecyl trimethyl ammonium bromide to the pyrrole monomer is 1: 3-3: 2, and the concentration of the pyrrole monomer in the dilute hydrochloric acid is 1.48 g/L.
Further, the initiator is ammonium persulfate, and the mass ratio of the added ammonium persulfate to the pyrrole monomer is 1: 1.
Further, chloride ion-doped polypyrrole nanowires (PPyNWs-Cl) and Ti3C2TxThe mixing mass ratio of MXene in water is 1: 2-3: 1.
A preparation method of the broadband adjustable composite wave-absorbing hydrogel specifically comprises the following steps:
(1) mixing polypyrrole nano-wire (PPyNWs-Cl) doped with chloride ions and Ti3C2TxMXene is added into deionized water, and the self-assembly Ti is prepared by ultrasonic, stirring, self-assembly and drying3C2Tx MXene。
(2) Mixing water and glycerol, adding acrylamide, N-methylene bisacrylamide, tetramethylethylenediamine and self-assembled Ti3C2TxMixing MXene uniformly;
(3) adding ammonium persulfate solution, rapidly stirring, and polymerizing to obtain Polyacrylamide (PAM) hydrogel precursor solution;
(4) and transferring the precursor solution to a mold, and reacting for 0.5-3 h in an oven at a constant temperature of 30-50 ℃. And removing residual reactants after the reaction is finished to prepare the broadband adjustable composite wave-absorbing hydrogel.
Further, in the step 2, the total volume of a mixed solvent composed of water and glycerol is 10 mL; the water content of the hydrogel is controlled by adjusting the volume ratio of water to glycerol.
Further, the volume ratio of water to glycerol is 2: 8-4: 6.
In step 3, the concentrations of acrylamide, N-methylene-bisacrylamide, ammonium persulfate and tetramethylethylenediamine in the system are 1mol/L, 0.030mol/L, 0.015mol/L and 0.007mol/L respectively.
The invention has the beneficial effects that:
the broadband controllable wave-absorbing hydrogel provided by the invention has an excellent electromagnetic wave absorption effect, the comprehensive performance is obviously improved, and the application prospect is wide. Meanwhile, the water content of the hydrogel is controlled by changing the volume ratio of water to glycerol in the liquid phase, so that the regulation and control of the wave-absorbing frequency band and the wave-absorbing strength can be achieved.
The invention provides a preparation method of broadband controllable wave-absorbing hydrogel, which is a method for doping and molding polyacrylamide hydrogel at one time. The used preparation raw materials are good in environmental friendliness, and the obtained hydrogel is excellent in wave-absorbing performance, good in adhesive performance and good in comprehensive performance, and can be applied to wave-absorbing hydrogel coatings.
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FIG. 1 shows non-self-assembled Ti3C2TxPure Polyacrylamide (PAM) hydrogel (a) with MXene filler and water content of 30% and self-assembled Ti3C2TxA PAM hydrogel (b) with 30% water content of MXene filler;
FIG. 2 is a graph of the reflection loss of a hydrogel having a thickness of 2.36mm in the X band (left) and Ku band (right), respectively;
FIG. 3 is a graph of the reflection loss of a 2.70mm thick hydrogel in the X band (left) and Ku band (right), respectively;
fig. 4 is a graph of the reflection loss of a loaded self-assembled MXene paraffin-only ring with a thickness of 3.94 mm.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources or can be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The MXene material used in the following examples is a single layer of Ti3C2 TxNanosheets, but not limited thereto; polypyrrole was in the form of a chloride-doped nanowire (PPyNWs-Cl).
The invention is described in further detail below with reference to the following figures and specific embodiments:
example 1
One, self-assembly type Ti3C2TxPreparation of MXene conductive filler
(1) Preparation of less-layer Ti3C2TxMXene powder:
adding 1.6g of lithium fluoride and 20ml of 75% diluted hydrochloric acid solution into a polytetrafluoroethylene reaction kettle, and magnetically stirring for 10 min; slowly add 1g MAX Ti3AlC2Reacting for 24 hours in a water bath at 35 ℃; washing with deionized water until pH is 7, ultrasonically dispersing, centrifuging, and taking the upper suspension to obtain MXene dispersion liquid. Freeze drying the dispersion to obtain Ti with less layer3C2TxMXene powder.
(2) Preparation of chloride-doped polypyrrole nanowire (PPyNWs-Cl) powder:
taking 125ml of 0.2M dilute hydrochloric acid, adding 0.91g of hexadecyl trimethyl ammonium bromide and 0.2g of pyrrole, and stirring for 2 hours at 1 ℃; dropwise adding 10ml of 0.3mol/ml ammonium persulfate solution, and continuously stirring and polymerizing for 24 hours; and filtering and washing the black solid precipitate until the pH value is 7, and freeze-drying to obtain the polypyrrole nanowire doped with chloride ions.
(3) Will reduce Ti layer3C2TxMXene powder and PPyNWs-Cl powder are added into a reactor in a mass ratio of 1:2 of 100Dispersing in mL water by ultrasonic for 30min, and magnetically stirring for 30 min. Drying in a vacuum oven at 40 ℃ for 12h to obtain the self-assembled Ti3C2TxMXene powder.
Preparation of composite hydrogel
(1) Mixing water and glycerol according to the volume ratio of 2:8 to obtain 10mL of liquid phase;
(2) weighing 107mg of self-assembled Ti3C2TxAdding MXene powder into the liquid phase, and performing ultrasonic dispersion for 30 min;
(3) weighing 0.71g of acrylamide and 48mg of N, N-dimethyl bisacrylamide, adding the weighed materials into the liquid phase, and stirring for 30 min;
(4) 15 mu L of tetramethylethylenediamine is sucked and added into the mixed solution of the step (3), and the mixture is continuously stirred for 10 min;
(5) adding 0.5mL of 0.61mol/L ammonium persulfate solution, and stirring for 30s to prepare a PAM hydrogel precursor solution;
(6) and transferring the precursor solution into a mold, placing the mold in a drying oven at 40 ℃, reacting for 1h at a constant temperature, washing with deionized water, and performing etching to obtain the controllable broadband wave-absorbing hydrogel.
Through the test of a vector network tester, the frequency band of electromagnetic waves is within the range of 8.2-18 GHz, the minimum reflection loss is-25 dB when the simulation thickness of the embodiment 1 is 2.36mm, and the effective wave-absorbing bandwidth is 4.3 GHz.
Example 2
One, self-assembly type Ti3C2TxPreparation of MXene conductive filler
(1) Preparation of less-layer Ti3C2TxMXene powder;
detailed preparation procedure and parameters as in example 1
(2) Preparing chloride ion doped polypyrrole nano-wire (PPyNWs-Cl) powder;
detailed preparation procedure and parameters as in example 1
(3) Will reduce Ti layer3C2TxMXene powder and PPyNWs-Cl powder are added into 100mL of water according to the mass ratio of 1:2, ultrasonically dispersed for 30min, and magnetically stirred for 30 min. Drying in a vacuum oven at 40 ℃ for 12h to obtain the self-assembled Ti3C2TxMXene powder.
Preparation of composite hydrogel
(1) Mixing water and glycerol according to the volume ratio of 3:7 to obtain 10mL of liquid phase;
(2) weighing 107mg of self-assembled Ti3C2TxAdding MXene powder into the liquid phase, and performing ultrasonic dispersion for 30 min;
(3) weighing 0.71g of acrylamide and 48mg of N, N-dimethyl bisacrylamide, adding the weighed materials into the liquid phase, and stirring for 30 min;
(4) adding 15 mu L of tetramethylethylenediamine into the mixed solution of the step (3), and continuously stirring for 10 min;
(5) adding 0.5mL of 0.61mol/L ammonium persulfate solution, and stirring for 30s to prepare a PAM hydrogel precursor solution;
(6) and transferring the precursor solution into a mold, placing the mold in a drying oven at 40 ℃, reacting for 1h at a constant temperature, washing with deionized water, and performing etching to obtain the controllable broadband wave-absorbing hydrogel.
Through the test of a vector network tester, the frequency band of electromagnetic waves is within the range of 8.2-18 GHz, the minimum reflection loss is-71 dB when the simulation thickness is 2.36mm, and the effective wave-absorbing bandwidth is 8.1 GHz.
Example 3
One, self-assembly type Ti3C2TxPreparation of MXene conductive filler
(1) Preparation of less-layer Ti3C2TxMXene powder;
detailed preparation procedure and parameters as in example 1
(2) Preparing chloride ion doped polypyrrole nano-wire (PPyNWs-Cl) powder;
detailed preparation procedure and parameters as in example 1
(3) Will reduce Ti layer3C2TxMXene powder and PPyNWs-Cl powder are added into 100mL of water according to the mass ratio of 1:2, ultrasonically dispersed for 30min, and magnetically stirred for 30 min. Drying in a vacuum oven at 40 ℃ for 12h to obtain the self-assembled Ti3C2TxMXene powder.
Preparation of composite hydrogel
(1) Mixing water and glycerol according to the volume ratio of 4:6 to obtain 10mL of liquid phase;
(2) weighing 107mg of self-assembled Ti3C2TxAdding MXene powder into the liquid phase, and performing ultrasonic dispersion for 30 min;
(3) weighing 0.71g of acrylamide and 48mg of N, N-dimethyl bisacrylamide, adding the weighed materials into the liquid phase, and stirring for 30 min;
(4) adding 15 mu L of tetramethylethylenediamine into the mixed solution of the step (3), and continuously stirring for 10 min;
(5) adding 0.5mL of 0.61mol/L ammonium persulfate solution, and stirring for 30s to prepare a PAM hydrogel precursor solution;
(6) and transferring the precursor solution into a mold, placing the mold in a drying oven at 40 ℃, reacting for 1h at a constant temperature, washing with deionized water, and performing etching to obtain the controllable broadband wave-absorbing hydrogel.
Through the test of a vector network tester, the frequency band of the electromagnetic wave is within the range of 8.2-18 GHz, the minimum reflection loss is-19 dB when the simulation thickness is 2.36mm, and the effective wave-absorbing bandwidth is 3.3 GHz.
Example 4
One, self-assembly type Ti3C2TxPreparation of MXene conductive filler
(1) Preparation of less-layer Ti3C2TxMXene powder;
detailed preparation procedure and parameters as in example 1
(2) Preparing chloride ion doped polypyrrole nano-wire (PPyNWs-Cl) powder;
wherein, the mole ratio of hexadecyl trimethyl ammonium bromide to pyrrole monomer is 3:2, other parameters and detailed preparation process are the same as those of the example 1
(3) Will reduce Ti layer3C2TxMXene powder and PPyNWs-Cl powder are added into 100mL of water according to the mass ratio of 2:1, ultrasonically dispersed for 30min, and magnetically stirred for 30 min. Drying in a vacuum oven at 40 ℃ for 12h to obtain the self-assembled Ti3C2TxMXene powder.
Preparation of composite hydrogel
(1) Mixing water and glycerol according to the volume ratio of 3:7 to obtain 10mL of liquid phase;
(2) weighing 107mg of self-assembled Ti3C2TxAdding MXene powder into the liquid phase, and performing ultrasonic dispersion for 30 min;
(3) weighing 0.71g of acrylamide and 48mg of N, N-dimethyl bisacrylamide, adding the weighed materials into the liquid phase, and stirring for 30 min;
(4) adding 15 mu L of tetramethylethylenediamine into the mixed solution of the step (3), and continuously stirring for 10 min;
(5) adding 0.5mL of 0.61mol/L ammonium persulfate solution, and stirring for 30s to prepare a PAM hydrogel precursor solution;
(6) and transferring the precursor solution into a mold, placing the mold in a 50 ℃ oven, reacting for 0.5h at a constant temperature, washing with deionized water, and etching to obtain the controllable broadband wave-absorbing hydrogel.
Through the test of a vector network analyzer, the controllable broadband wave-absorbing hydrogel has good wave-absorbing performance.
Comparative example 1
Preparation of polyacrylamide hydrogel
(1) Weighing 0.71g of acrylamide powder and 48mg of N, N-dimethyl bisacrylamide powder, adding into 10mL of deionized water, and stirring for 30 min;
(2) adding 10 mu L of tetramethylethylenediamine into the mixed solution obtained in the previous step, and continuously stirring for 10 min;
(3) adding 0.5mL of 10mmol/mL ammonium persulfate solution, and stirring for 30s to obtain a PAM hydrogel precursor solution;
(4) and transferring the precursor solution into a mold, placing the mold in a drying oven at 40 ℃, reacting for 1h at constant temperature, washing the mold with deionized water, and etching to obtain the pure PAM hydrogel.
Through the test of a vector network analyzer, the electromagnetic wave frequency band is in the range of 8.2-18 GHz, the minimum reflection loss is-6 dB when the simulation thickness is 2.36mm, and no effective wave-absorbing bandwidth exists.
FIG. 1 shows non-self-assembled Ti of comparative example 13C2TxPure Polyacrylamide (PAM) hydrogel with 30% water content of MXene filler (a) and example 2 with addition of self-assembled Ti3C2TxMaterial of PAM hydrogel (b) with MXene filler water content of 30%, and figure 2 and figure 3 are respectively comparativeComparative results of the reflection loss measurements for different thicknesses of the hydrogels of example 1 and examples 1-3. As can be seen from fig. 2, the hydrogel loaded with MXene and polypyrrole nanowires has significantly enhanced electromagnetic wave absorption performance.
As can be seen by comparing the performance test results shown in the attached figures 2 and 3, the minimum reflection loss occurrence position and the wave-absorbing frequency band of the composite hydrogel can be adjusted by adjusting the water content of the system, so that the purpose of adjustable wave-absorbing performance is achieved.
The reflection loss curve of the self-assembled MXene powder is obtained by a coaxial method test. The load capacity of the self-assembled MXene of the prepared coaxial ring is consistent with that of the coaxial ring in the embodiment 1-3; after simulation, the reflection loss was minimized at a simulated thickness of 3.94mm and plotted against this data to obtain figure 4. Compared with the prior art, the single self-assembled MXene wave-absorbing material has the advantages that the wave-absorbing performance is far lower than that of a composite system, the high content and the large thickness are required, and the requirements of thinness, lightness, width and strength of the wave-absorbing material are not met.
According to the invention, polyacrylamide hydrogel is taken as a matrix, and composite filler obtained after self-assembly of MXene nanosheets and polypyrrole nanowires is added into the system before gelation reaction, so that the novel wave-absorbing hydrogel is obtained. The composite hydrogel prepared by the method has the characteristics of high wave-absorbing strength, adjustable wave-absorbing frequency band and the like. The preparation method of the wave-absorbing hydrogel is simple and easy to implement, low in energy consumption, time-saving, material-saving and good in repeatability, and the constructed controllable broadband wave-absorbing hydrogel can be applied to the field of electronic equipment. For example, the broadband controllable wave-absorbing hydrogel provided by the invention can be used as a coating of electronic equipment to play a role in absorbing electromagnetic waves.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.

Claims (8)

1. A broadband adjustable composite wave-absorbing hydrogel is characterized in that: the broadband adjustable composite wave-absorbing hydrogel is formed by self-assemblyAssembling type Ti3C2TxMXene and polyacrylamide hydrogel, wherein the self-assembly type Ti is3C2TxThe content of MXene is 1-30 wt%, and the water content of the polyacrylamide hydrogel is 20-40 vol%. The self-assembled Ti3C2TxPolypyrrole nanowire (PPyNWs-Cl) doped with chloride ion by MXene and Ti3C2TxMXene is formed by self-assembly in water.
2. The broadband tunable composite wave-absorbing hydrogel of claim 1, wherein: the polypyrrole nanowire doped with chloride ions is generated by initiating polymerization of a pyrrole monomer dissolved in 0.2M dilute hydrochloric acid and hexadecyl trimethyl ammonium bromide in an ice bath through an initiator, wherein the hexadecyl trimethyl ammonium bromide is used as a soft template, the molar ratio of the hexadecyl trimethyl ammonium bromide to the pyrrole monomer is 1: 3-3: 2, and the concentration of the pyrrole monomer in the dilute hydrochloric acid is 1.48 g/L.
3. The broadband tunable composite wave-absorbing hydrogel of claim 2, wherein: the initiator used for polymerization of the polypyrrole nanowire doped with the chloride ions is ammonium persulfate, and the mass ratio of the added ammonium persulfate to the pyrrole monomer is 1: 1.
4. The broadband tunable composite wave-absorbing hydrogel of claim 1, wherein: chloride ion doped polypyrrole nanowires (PPyNWs-Cl) and Ti3C2TxThe mixing mass ratio of MXene in water is 1: 2-3: 1.
5. A method for preparing the broadband adjustable composite wave-absorbing hydrogel of any one of claims 1 to 4, which is characterized in that: the method specifically comprises the following steps:
(1) polypyrrole nanowire doped with chloride ion (PPyNWs) and Ti3C2TxMXene is added into deionized water, and the self-assembly Ti is prepared by ultrasonic, stirring, self-assembly and drying3C2Tx MXene。
(2) Mixing water and glycerol, adding acrylamide, N-methylene bisacrylamide, tetramethylethylenediamine and self-assembled Ti3C2TxMixing MXene uniformly;
(3) adding ammonium persulfate solution, rapidly stirring, and polymerizing to obtain Polyacrylamide (PAM) hydrogel precursor solution;
(4) and transferring the precursor solution to a mold, and reacting for 0.5-3 h in an oven at a constant temperature of 30-50 ℃. And removing residual reactants after the reaction is finished to prepare the broadband adjustable composite wave-absorbing hydrogel.
6. The method of claim 5, wherein: in the step 2, the total volume of a mixed solvent consisting of water and glycerol is 10 mL; the water content of the hydrogel is controlled by adjusting the volume ratio of water to glycerol.
7. The method of claim 6, wherein: the volume ratio of the water to the glycerol is 2: 8-4: 6.
8. The method of claim 5, wherein: in the step 3, the concentrations of acrylamide, N-methylene-bisacrylamide, ammonium persulfate and tetramethylethylenediamine in the system are respectively 1mol/L, 0.030mol/L, 0.015mol/L and 0.007 mol/L.
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