CN116356573A - Polyaniline modified graphene composite wave-absorbing fiber fabric, preparation method and application - Google Patents
Polyaniline modified graphene composite wave-absorbing fiber fabric, preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract
The invention discloses a polyaniline modified graphene composite wave-absorbing fiber fabric, a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1: mixing aramid fiber and alkali to prepare a solution, obtaining a dispersion liquid, and fully mixing and reacting to obtain aramid nanofiber; step 2: preparing graphene oxide dispersion liquid; step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning stock solution, spinning into fibers by adopting a wet spinning method, braiding the fibers into fabrics, and reducing to obtain graphene aramid nanofiber composite fabrics; step 4: adding an aniline monomer and the fabric obtained in the step 3 into an acid solution for soaking for T time, adding an ammonium persulfate solution for polymerization reaction, and cleaning and drying to obtain the polyaniline modified graphene composite wave-absorbing fiber fabric; the polyaniline modified graphene composite fiber fabric obtained by the invention has excellent wave absorbing performance, and the wave absorbing performance of the polyaniline modified graphene composite fiber fabric can be remarkably improved by in-situ growth of doped polyaniline on the surface of the RANF30 composite fiber.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a polyaniline modified graphene composite wave-absorbing fiber fabric, a preparation method and application.
Background
In recent years, with the intellectualization of electronic devices, there is an increasing interest in functional wearable fabrics. The wearable electronic fabric equipment can monitor various indexes of a human body in real time, effectively collect human body information and is beneficial to the healthy development of the human body. The product relates to a plurality of aspects of leading edge research in the fields of sensors, medical care, electronic displays, intelligent textiles, the Internet of things and the like. Graphene has the advantages of high conductivity, low density, large specific surface area and the like, and is widely applied to the field.
Most of researches at present aim at coating graphene on cotton fabric through an impregnation method, so that the requirements on flexibility, air permeability and the like of wearable equipment can be met, and the performance of the filler can be maintained. The rough structure of the cotton fabric surface can increase the adhesiveness of graphene on the fabric surface in terms of microstructure. In addition, a large number of oxygen-containing functional groups on the surface of the graphene oxide can form a physical or chemical crosslinking effect with the surface of the fabric, so that the adhesiveness of the surface of the fabric is remarkably improved. However, after long-time repeated cleaning, the nano particles on the surface of the cotton fabric are gradually reduced, so that the performance is poorer and poorer. Therefore, it is particularly important to provide a functional fabric with good stability and long cycle life. At present, the graphene fiber has the problems of large brittleness, insufficient toughness and the like, is difficult to directly weave into a fabric, and limits the practical application of the graphene fiber, so that the flexibility and the functionality of the graphene-based wave-absorbing fiber fabric are the current research hot spot.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a polyaniline modified graphene composite wave-absorbing fiber fabric with excellent wave-absorbing and mechanical properties, a preparation method and application thereof.
A preparation method of polyaniline modified graphene composite wave-absorbing fiber fabric comprises the following steps:
step 1: mixing aramid fiber and alkali to prepare a solution, obtaining a dispersion liquid, and fully mixing and reacting to obtain aramid nanofiber;
step 2: preparing graphene oxide dispersion liquid;
step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning stock solution, spinning into fibers by adopting a wet spinning method, braiding the fibers into fabrics, and reducing to obtain graphene aramid nanofiber composite fabrics; the mass ratio of the aramid nanofiber to the graphene oxide is as follows: 10:3;
step 4: adding an aniline monomer and the fabric obtained in the step 3 into an acid solution for soaking for T time, adding an ammonium persulfate solution for polymerization reaction, and cleaning and drying to obtain the polyaniline modified graphene composite wave-absorbing fiber fabric; wherein the mass ratio of the aniline monomer to the fabric in the step 3 is as follows: 10:1; the mass ratio of ammonium persulfate to aniline monomer is as follows: 1:1.
Further, in the step 1, KOH is adopted as the alkali, and the concentration of the aramid fiber in the dispersion liquid is 20mg/mL.
Further, the concentration of graphene oxide in the graphene oxide dispersion liquid in the step 2 is 10mg/mL, and the size of the graphene oxide lamellar is 30-50 mu m.
Furthermore, the coagulating liquid in the wet spinning in the step 3 is a mixed solution formed by hydrochloric acid and deionized water, and the volume ratio of the hydrochloric acid to the deionized water is 1:50; the extrusion speed of the spinning dope was 1mL/min, and the spin coagulation bath was 10r/min.
Further, the conditions for the reduction in the step 3 are as follows: the hydroiodic acid was reduced at 40℃for 24 hours.
Further, in the step 4, the soaking time of the aniline monomer and the fabric in the acid solution is 24 hours, the polymerization reaction temperature is 0 ℃, and the reaction time is 6 hours.
Further, the acid solution in the step 4 is hydrochloric acid aqueous solution.
Further, the concentration of the aqueous hydrochloric acid solution is 0.2mol/L to 2.0mol/L.
The polyaniline modified graphene composite wave-absorbing fiber fabric prepared by the preparation method is characterized in that polyaniline is tightly adhered to the surface of the graphene composite fiber fabric to form a compact polyaniline nano-layer; polyaniline has uniform particle size, particles are closely stacked and intertwined together in a rod-shaped structure to form a net-shaped structure.
The application of the polyaniline modified graphene composite wave-absorbing fiber fabric is that the polyaniline modified graphene composite wave-absorbing fiber fabric is used for preparing the wave-absorbing fabric.
The beneficial effects of the invention are as follows:
(1) The polyaniline modified graphene composite wave-absorbing fiber fabric obtained by the invention has excellent wave-absorbing performance, and the wave-absorbing performance of the polyaniline-doped graphene composite wave-absorbing fiber fabric can be remarkably improved by in-situ growth of the polyaniline-doped graphene on the surface of the RANF30 composite fiber.
(2) The wave-absorbing fabric prepared by the invention has the RL at the frequency of 12.8GHz when the thickness of RANF30-0.9 is 2.8mm in the Ku wave band min -59.4dB, eab=4.9 GHz (12-16.9 GHz). Furthermore, when the thickness is 2.6mm, there is a maximum absorption bandwidth, the EAB thereof max =6ghz (12-18 GHz), realizing complete coverage in the X and Ku bands, meeting the use requirement of 'thin, light, wide and strong';
(3) The polyaniline modified graphene composite wave-absorbing fiber fabric has the performances of flexibility, high temperature resistance, corrosion resistance and the like.
Drawings
Fig. 1 is an SEM image of the polyaniline-modified graphene composite wave-absorbing fiber fabric obtained in examples 1 to 5 of the present invention.
Fig. 2 is an XRD pattern of the polyaniline-modified graphene composite wave-absorbing fiber fabric obtained in examples 1 to 5 of the present invention.
Fig. 3 is an FTIR diagram of the polyaniline-modified graphene composite wave-absorbing fiber fabric obtained in examples 1 to 5 of the present invention.
Fig. 4 is a schematic diagram of electromagnetic parameters of polyaniline modified graphene composite wave-absorbing fiber fabrics obtained in examples 1 to 5 of the present invention.
Fig. 5 is a three-dimensional reflection loss diagram of polyaniline-modified graphene composite wave-absorbing fiber fabrics obtained in examples 1 to 5 according to the present invention at different thicknesses.
Fig. 6 is an impedance matching chart of polyaniline modified graphene composite wave-absorbing fiber fabrics obtained in examples 1 to 5 of the present invention at different thicknesses.
Fig. 7 shows the attenuation constants of the polyaniline-modified graphene composite wave-absorbing fiber fabrics obtained in examples 1 to 5 of the present invention.
FIG. 8 is a Cole-Cole curve of the polyaniline-modified graphene composite wave-absorbing fiber fabrics obtained in examples 1-5 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and specific examples.
A preparation method of polyaniline modified graphene composite wave-absorbing fiber fabric comprises the following steps:
step 1: adding aramid fiber and KOH into DMSO, mixing to prepare a solution, obtaining an ANF dispersion liquid with the concentration of 20mg/mL, and magnetically stirring the mixed dispersion liquid at the stirring speed of 500r/min for one week at room temperature to gradually change from colorless to dark red.
Step 2: preparing graphene oxide dispersion liquid; and (3) pre-freezing the graphene oxide GO aqueous dispersion liquid into a solid state by using liquid nitrogen, wherein the size of the GO sheet layer is 30-50 mu m, and putting the solid state into a vacuum freeze dryer for freeze drying for 48 hours to obtain dry GO powder. The GO powder was added to DMSO to give a uniformly dispersed dispersion of GO (DMSO) at a concentration of 10 mg/mL.
Step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning solution, wherein the total system concentration in the spinning solution is 15mg/mL; spinning into fibers by adopting a wet spinning method, weaving the fibers into fabrics, and reducing to obtain the graphene aramid nanofiber composite fabrics; the mass ratio of the aramid nanofiber to the graphene oxide is as follows: 10:3; the coagulating bath is a mixed solution of hydrochloric acid and deionized water, and the volume ratio is 1:50. The spinning dope was extruded at a speed of 1mL/min, the coagulation bath was rotated at 10r/min, and after the fiber was coagulated, it was removed from the coagulation bath and washed 3 times with deionized water and dried at room temperature until the solvent was completely removed to give ANF30. The dried fiber was woven into a fabric, which was placed in an oven at 40 ℃ for 24 hours with hydroiodic acid, and then the reduced fiber or fabric was cleaned and designated as RANF30.
Step 4: adding an aniline monomer and the fabric obtained in the step 3 into hydrochloric acid solution for soaking for 24 hours, then adding APS solution at 0 ℃ for polymerization reaction for 6 hours, and then cleaning and drying to obtain polyaniline modified graphene composite wave-absorbing fiber fabric; wherein the mass ratio of the aniline monomer to the fabric in the step 3 is as follows: 10:1; the mass ratio of ammonium persulfate to aniline monomer is as follows: 1:1; the concentration of the hydrochloric acid solution is 0.2-2.0 mol/L.
Example 1
A preparation method of polyaniline modified graphene composite wave-absorbing fiber fabric comprises the following steps:
step 1: 2g of aramid fiber and 2g of KOH were added to 100mL of DMSO and mixed to prepare a solution, to obtain an ANF dispersion having a concentration of 20mg/mL, and the dispersion was stirred magnetically at a stirring speed of 500r/min at room temperature for one week and then changed from colorless to dark red gradually.
Step 2: preparing graphene oxide dispersion liquid; and (3) pre-freezing the graphene oxide GO aqueous dispersion (directly purchased) with the GO lamellar size of 30-50 mu m into a solid state by using liquid nitrogen, and freeze-drying for 48 hours in a vacuum freeze dryer to obtain dry GO powder. 100mg of GO powder was added to 10mL of DMSO to give a uniformly dispersed dispersion of GO (DMSO) at a concentration of 10 mg/mL.
Step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning solution, wherein the total system concentration in the spinning solution is 15mg/mL; spinning into fibers by adopting a wet spinning method, weaving the fibers into fabrics, and reducing to obtain the graphene aramid nanofiber composite fabrics; the mass ratio of the aramid nanofiber to the graphene oxide is as follows: 10:3; the coagulating bath is a mixed solution of hydrochloric acid and deionized water, and the volume ratio is 1:50. The spinning dope was extruded at a speed of 1mL/min, the coagulation bath was rotated at 10r/min, and after the fiber was coagulated, it was removed from the coagulation bath and washed 3 times with deionized water and dried at room temperature until the solvent was completely removed. The dried fiber was woven into a fabric, which was placed in an oven at 40 ℃ for 24 hours with hydroiodic acid, and then the reduced fiber or fabric was cleaned and designated as RANF30.
Step 4: adding an aniline monomer (ANi) and the fabric obtained in the step 3 into a hydrochloric acid solution with the concentration of 0.2mol/L, soaking for 24 hours, adding an APS solution at the temperature of 0 ℃ for polymerization reaction for 6 hours, and then washing and drying to obtain the polyaniline modified graphene composite wave-absorbing fiber fabric (RANF 30-0.2); wherein the mass ratio of the aniline monomer to the fabric in the step 3 is as follows: 10:1; the mass ratio of ammonium persulfate to aniline monomer is as follows: 1:1.
Example 2
A preparation method of polyaniline modified graphene composite wave-absorbing fiber fabric comprises the following steps:
step 1: 2g of aramid fiber and 2g of KOH were added to 100mL of DMSO and mixed to prepare a solution, to obtain an ANF dispersion having a concentration of 20mg/mL, and the dispersion was stirred magnetically at a stirring speed of 500r/min at room temperature for one week and then changed from colorless to dark red gradually.
Step 2: preparing graphene oxide dispersion liquid; and (3) pre-freezing the graphene oxide GO aqueous dispersion (directly purchased) with the GO lamellar size of 30-50 mu m into a solid state by using liquid nitrogen, and freeze-drying for 48 hours in a vacuum freeze dryer to obtain dry GO powder. 100mg of GO powder was added to 10mL of DMSO to give a uniformly dispersed dispersion of GO (DMSO) at a concentration of 10 mg/mL.
Step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning solution, wherein the total system concentration in the spinning solution is 15mg/mL; spinning into fibers by adopting a wet spinning method, weaving the fibers into fabrics, and reducing to obtain the graphene aramid nanofiber composite fabrics; the mass ratio of the aramid nanofiber to the graphene oxide is as follows: 10:3; the coagulating bath is a mixed solution of hydrochloric acid and deionized water, and the volume ratio is 1:50. The spinning dope was extruded at a speed of 1mL/min, the coagulation bath was rotated at 10r/min, and after the fiber was coagulated, it was removed from the coagulation bath and washed 3 times with deionized water and dried at room temperature until the solvent was completely removed. The dried fiber was woven into a fabric, which was placed in an oven at 40 ℃ for 24 hours with hydroiodic acid, and then the reduced fiber or fabric was cleaned and designated as RANF30.
Step 4: adding an aniline monomer (ANi) and the fabric obtained in the step 3 into a hydrochloric acid solution with the concentration of 0.5mol/L, soaking for 24 hours, adding an APS solution at the temperature of 0 ℃ for polymerization reaction for 6 hours, and then washing and drying to obtain the polyaniline modified graphene composite wave-absorbing fiber fabric (RANF 30-0.5); wherein the mass ratio of the aniline monomer to the fabric in the step 3 is as follows: 10:1; the mass ratio of ammonium persulfate to aniline monomer is as follows: 1:1.
Example 3
A preparation method of polyaniline modified graphene composite wave-absorbing fiber fabric comprises the following steps:
step 1: 2g of aramid fiber and 2g of KOH were added to 100mL of DMSO and mixed to prepare a solution, to obtain an ANF dispersion having a concentration of 20mg/mL, and the dispersion was stirred magnetically at a stirring speed of 500r/min at room temperature for one week and then changed from colorless to dark red gradually.
Step 2: preparing graphene oxide dispersion liquid; and (3) pre-freezing the graphene oxide GO aqueous dispersion (directly purchased) with the GO lamellar size of 30-50 mu m into a solid state by using liquid nitrogen, and freeze-drying for 48 hours in a vacuum freeze dryer to obtain dry GO powder. 100mg of GO powder was added to 10mL of DMSO to give a uniformly dispersed dispersion of GO (DMSO) at a concentration of 10 mg/mL.
Step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning solution, wherein the total system concentration in the spinning solution is 15mg/mL; spinning into fibers by adopting a wet spinning method, weaving the fibers into fabrics, and reducing to obtain the graphene aramid nanofiber composite fabrics; the mass ratio of the aramid nanofiber to the graphene oxide is as follows: 10:3; the coagulating bath is a mixed solution of hydrochloric acid and deionized water, and the volume ratio is 1:50. The spinning dope was extruded at a speed of 1mL/min, the coagulation bath was rotated at 10r/min, and after the fiber was coagulated, it was removed from the coagulation bath and washed 3 times with deionized water and dried at room temperature until the solvent was completely removed. The dried fiber was woven into a fabric, which was placed in an oven at 40 ℃ for 24 hours with hydroiodic acid, and then the reduced fiber or fabric was cleaned and designated as RANF30.
Step 4: adding an aniline monomer (ANi) and the fabric obtained in the step 3 into a hydrochloric acid solution with the concentration of 0.9mol/L, soaking for 24 hours, adding an APS solution at the temperature of 0 ℃ for polymerization reaction for 6 hours, and then washing and drying to obtain the polyaniline modified graphene composite wave-absorbing fiber fabric (RANF 30-0.9); wherein the mass ratio of the aniline monomer to the fabric in the step 3 is as follows: 10:1; the mass ratio of ammonium persulfate to aniline monomer is as follows: 1:1.
Example 4
A preparation method of polyaniline modified graphene composite wave-absorbing fiber fabric comprises the following steps:
step 1: 2g of aramid fiber and 2g of KOH were added to 100mL of DMSO and mixed to prepare a solution, to obtain an ANF dispersion having a concentration of 20mg/mL, and the dispersion was stirred magnetically at a stirring speed of 500r/min at room temperature for one week and then changed from colorless to dark red gradually.
Step 2: preparing graphene oxide dispersion liquid; and (3) pre-freezing the graphene oxide GO aqueous dispersion (directly purchased) with the GO lamellar size of 30-50 mu m into a solid state by using liquid nitrogen, and freeze-drying for 48 hours in a vacuum freeze dryer to obtain dry GO powder. 100mg of GO powder was added to 10mL of DMSO to give a uniformly dispersed dispersion of GO (DMSO) at a concentration of 10 mg/mL.
Step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning solution, wherein the total system concentration in the spinning solution is 15mg/mL; spinning into fibers by adopting a wet spinning method, weaving the fibers into fabrics, and reducing to obtain the graphene aramid nanofiber composite fabrics; the mass ratio of the aramid nanofiber to the graphene oxide is as follows: 10:3; the coagulating bath is a mixed solution of hydrochloric acid and deionized water, and the volume ratio is 1:50. The spinning dope was extruded at a speed of 1mL/min, the coagulation bath was rotated at 10r/min, and after the fiber was coagulated, it was removed from the coagulation bath and washed 3 times with deionized water and dried at room temperature until the solvent was completely removed. The dried fiber was woven into a fabric, which was placed in an oven at 40 ℃ for 24 hours with hydroiodic acid, and then the reduced fiber or fabric was cleaned and designated as RANF30.
Step 4: adding an aniline monomer (ANi) and the fabric obtained in the step 3 into a hydrochloric acid solution with the concentration of 1.4mol/L, soaking for 24 hours, adding an APS solution at the temperature of 0 ℃ for polymerization reaction for 6 hours, and then washing and drying to obtain the polyaniline modified graphene composite wave-absorbing fiber fabric (RANF 30-1.4); wherein the mass ratio of the aniline monomer to the fabric in the step 3 is as follows: 10:1; the mass ratio of ammonium persulfate to aniline monomer is as follows: 1:1.
Example 5
A preparation method of polyaniline modified graphene composite wave-absorbing fiber fabric comprises the following steps:
step 1: 2g of aramid fiber and 2g of KOH were added to 100mL of DMSO and mixed to prepare a solution, to obtain an ANF dispersion having a concentration of 20mg/mL, and the dispersion was stirred magnetically at a stirring speed of 500r/min at room temperature for one week and then changed from colorless to dark red gradually.
Step 2: preparing graphene oxide dispersion liquid; and (3) pre-freezing the graphene oxide GO aqueous dispersion (directly purchased) with the GO lamellar size of 30-50 mu m into a solid state by using liquid nitrogen, and freeze-drying for 48 hours in a vacuum freeze dryer to obtain dry GO powder. 100mg of GO powder was added to 10mL of DMSO to give a uniformly dispersed dispersion of GO (DMSO) at a concentration of 10 mg/mL.
Step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning solution, wherein the total system concentration in the spinning solution is 15mg/mL; spinning into fibers by adopting a wet spinning method, weaving the fibers into fabrics, and reducing to obtain the graphene aramid nanofiber composite fabrics; the mass ratio of the aramid nanofiber to the graphene oxide is as follows: 10:3; the coagulating bath is a mixed solution of hydrochloric acid and deionized water, and the volume ratio is 1:50. The spinning dope was extruded at a speed of 1mL/min, the coagulation bath was rotated at 10r/min, and after the fiber was coagulated, it was removed from the coagulation bath and washed 3 times with deionized water and dried at room temperature until the solvent was completely removed. The dried fiber was woven into a fabric, which was placed in an oven at 40 ℃ for 24 hours with hydroiodic acid, and then the reduced fiber or fabric was cleaned and designated as RANF30.
Step 4: adding an aniline monomer (ANi) and the fabric obtained in the step 3 into a hydrochloric acid solution with the concentration of 2.0mol/L, soaking for 24 hours, adding an APS solution at the temperature of 0 ℃ for polymerization reaction for 6 hours, and then washing and drying to obtain the polyaniline modified graphene composite wave-absorbing fiber fabric (RANF 30-2.0); wherein the mass ratio of the aniline monomer to the fabric in the step 3 is as follows: 10:1; the mass ratio of ammonium persulfate to aniline monomer is as follows: 1:1.
The polyaniline modified graphene composite wave-absorbing fiber fabrics obtained in examples 1 to 5 were subjected to performance test. Characterization of the morphology structure was performed on the samples using a field emission scanning electron microscope (FE-SEM, JEOL, JSM-7001F). Functional group structural characterization was performed using a Tensor II type Fourier transform infrared spectrometer (FTIR) transmission mode fiber from Bruker, germany, with a scanning range of 400-4000cm-1 and a scanning accuracy of 4cm-1. The samples such as fibers were subjected to characterization analysis of crystallinity and order by using a wide-angle X-ray diffractometer (XRD, PW1830, philips) from bruke, germany, the test details are as follows: the Cu target is irradiated by K alpha, the scanning range is 5-60 degrees, and the speed is 5 degrees/min. The composite fiber fabric was tested for its wave absorbing properties in the frequency range between 8-18GHz using a vector network analyzer (AV 3618, CETC). The samples were woven into rectangular fabrics of length 2.286cm, width 1.016cm and length 1.5799cm and width 0.7899cm, and the wave-absorbing properties in the range of 8-12GHz (X-band) and 12-18GHz (Ku-band), respectively, were tested by the waveguide method.
Fig. 1 is an SEM image of polyaniline adsorption on the fiber surface in the polyaniline-modified graphene composite wave-absorbing fiber fabrics obtained in examples 1 to 5. From the figure, the rough fiber surface can absorb more aniline monomers, provides synthesis sites for in-situ growth of polyaniline, and is favorable for forming polyaniline on the surface. After ammonium persulfate polymerization reaction, polyaniline is greenish black, and after the fiber is washed and dried, polyaniline particles are still closely attached to the surface of the fiber, so that a compact polyaniline nano-layer is formed. The polyaniline has uniform particle size distribution, particles are closely piled, and the particles are entangled together in a rod shape to form a net structure, so that a conductive path is formed, and the conductivity is improved. In the figure, a1 to a3 are the results of example 1, b1 to b3 are the results of example 2, c1 to c3 are the results of example 3, d1 to d3 are the results of example 4, and d1 to d3 are the results of example 5.
Fig. 2 is an XRD pattern of the polyaniline-modified graphene composite wave-absorbing fiber fabric obtained in examples 1 to 5 of the present invention, a is the polyaniline-modified graphene composite wave-absorbing fiber fabric, and b is the polyaniline result. As can be seen from the graph a, diffraction peaks appear at 20.4 degrees, 22.9 degrees and 28.2 degrees, which correspond to the (110), (200) crystal faces and (004) crystal faces of the aramid fiber respectively, and the positions and the shapes of the diffraction peaks are consistent with those of the RANF30, which indicates that in-situ growth of polyaniline does not change the crystal structure of the fiber. However, after in situ growth of polyaniline on the surface of the RANF30 fiber, the diffraction peak of polyaniline does not appear in the XRD pattern, because polyaniline is only a thin layer on the surface of the fiber, and the content is so small that the diffraction peak is not found by XRD test. As can be seen from fig. b, diffraction peaks appear at 8.6 °, 14.6 °, 20.5 °, 25.3 °, 26.9 °, corresponding to the (001), (011), (020), (200), (121) crystal planes of polyaniline, respectively. The diffraction peak has a broad peak shape, which indicates the amorphous structure of polyaniline. Along with the increase of the concentration of hydrochloric acid, the position and the shape of the diffraction peak of the doped polyaniline are not changed, and the diffraction peak shape is relatively sharp at 25.2 degrees, which shows that the crystallinity is relatively high, and the polyaniline orientation after proton acid doping has certain order.
Fig. 3 is an FTIR diagram of the polyaniline-modified graphene composite wave-absorbing fiber fabric obtained in examples 1 to 5 of the present invention. a is polyaniline modified graphene composite wave-absorbing fiber fabric, and b is polyaniline result. From figure a it can be seen that the presence of polyaniline does not change its peak position and that the FTIR profile is substantially consistent. 1563cm can be seen from FIG. b -1 、1486cm -1 Telescoping vibration of C=C in quinoid (N=Q=N) and benzoid (N-B-N) structures in polyaniline, respectively, 1300cm -1 、1242cm -1 The stretching vibration peaks of C-N, C =n, respectively, indicate successful preparation of polyaniline by hydrochloric acid doping and persulfateBoth the polyaniline benzene and quinone structures exist after the oxidation of ammonium acid. The peak positions of polyaniline are marked in the figure a, and in addition, no peak or few peaks are shown in the figure, which shows that polyaniline does not chemically react with the fiber surface, but only is physically adsorbed on the fiber surface, and the rough surface is favorable for compact growth, consistent with SEM analysis.
The ANF composite fiber before reduction is woven into rectangular fabrics (consistent with the sizes of waveguide cavities in X and Ku wave bands) with the lengths of 2.286cm, the widths of 1.016cm, the lengths of 1.5799cm and the widths of 0.7899cm respectively, and then the fabrics are reduced by hydroiodic acid, washed, dried and used for testing. From the electromagnetic parameters obtained by the test, a reflection loss value (RL) is calculated. Epsilon' represents the real part of the complex permittivity and epsilon "represents the imaginary part of the complex permittivity. Fig. 4 shows electromagnetic parameters of polyaniline modified graphene composite wave-absorbing fiber fabrics obtained in examples 1 to 5 in the X and Ku bands, it can be seen that, in the X and Ku bands, as the concentration of the hydrochloric acid doped polyaniline increases, the real part and the imaginary part of the dielectric constant show a trend of increasing and decreasing after increasing, and the electromagnetic parameters in the X band are greater than those in the Ku band, which is characterized in that the time for generating polarization under an alternating electric field lags the change time of the electric field frequency, thereby leading to gradual decrease of the real part and the imaginary part of the dielectric constant as the frequency increases. The polyaniline modified graphene composite wave-absorbing fiber fabric gradually increases in conductivity along with the increase of the doping concentration of hydrochloric acid, however, when the concentration of hydrochloric acid is further increased, the conductivity of the polyaniline modified graphene composite wave-absorbing fiber fabric gradually decreases, so that the real part and the imaginary part of the dielectric constant tend to increase first and then decrease. When hydrochloric acid is used as proton acid to dope eigenstate polyaniline, H in hydrochloric acid + Ionic and para-anionic Cl - Into the main chain of polyaniline, and combines with N atoms in amine and imine groups to form polar words and double polarized ions to be delocalized into a large pi bond of the whole molecular chain, thereby greatly enhancing the conductivity of polyaniline. Under the condition of the same oxidation degree, when the concentration of hydrochloric acid is too high, the benzene type structure of polyaniline is increased, the conductivity is reduced instead, and the conductivity of polyaniline is highest only when the oxidation state and the reduction state in doped polyaniline are the same. The dielectric material has a loss tangent value of c1 and c2, and the highest loss angle in the X-band RANF30-0.9The tangent value, in the Ku band, RANF30-0.5 has the highest loss tangent value, and the larger the loss tangent value, the stronger the loss ability to electromagnetic waves is, however, an excessively large loss tangent value causes impedance mismatch, which is detrimental to its wave absorbing performance.
The reflection loss values of the polyaniline modified graphene composite wave-absorbing fiber fabric in the X and Ku wave bands are calculated by adopting transmission line theory through electromagnetic parameters, and are shown in figure 5. The three-dimensional reflection loss values of RANF30/RANF30-0.2/RANF30-0.5/RANF30-0.9/RANF30-1.4/RANF30-2.0 are shown in FIG. 5 (a 1-f 1), respectively. With the increasing concentration of the hydrochloric acid doped polyaniline, in the X wave band, RL of all the composite fabrics min The values have smaller difference, are smaller than-10 dB, and show that the wave absorbing performance is achieved. In addition, EAB max Completely covers all frequency ranges of the X wave band, and shows that the broadband absorption performance is excellent. As the thickness of the material increases, RL min Gradually moving towards higher frequencies, which corresponds to the quarter wavelength theory. Therefore, the wave absorbing performance of the composite fabric under high frequency is tested, the graphs (a 2-f 2) are respectively RANF30/RANF30-0.2/RANF30-0.5/RANF30-0.9/RANF30-1.4/RANF30-2.0 three-dimensional reflection loss values in the Ku wave band, and it can be seen that the RL of the polyaniline modified graphene composite wave absorbing fiber fabric with the increase of the hydrochloric acid concentration min The increase is followed by a smaller increase. In particular RANF30-0.9 has the most excellent wave absorbing performance, and RL at a frequency of 12.8GHz at a thickness of 2.8mm min -59.4dB, eab=4.9 GHz (12-16.9 GHz). Furthermore, at a thickness of 2.6. 2.6mm, there is a maximum absorption bandwidth, EAB max =6 GHz (12-18 GHz), realizing complete coverage in Ku band, significantly better than the wave absorbing performance of pure RANF30 composite fabric without in-situ growth of polyaniline. In the X and Ku wave bands, the wave absorbing performance of the in-situ growth polyaniline doped RANF30 composite fabric is obviously superior to that of the pure RANF30 composite fabric, the full-wave band absorption in the X and Ku wave bands can be realized, especially the RANF30-0.9, the RLmin value reaches-59.4 dB, and the wave absorbing performance is excellent.
Fig. 6 is an impedance matching diagram of the polyaniline-modified graphene composite wave-absorbing fiber fabric obtained in examples 1 to 5 in the X and Ku bands. Impedance matching |Z in /Z 0 A value of 1 indicates the best impedance matching performance, and is generally considered to be when Z in /Z 0 The value of I is in the range of 0.8-1.2, and has better impedance matching performance. Fig. 6 (a 1-f 1) shows the impedance matching patterns of RANF30-0.2RANF30-0.5RANF30-0.9RANF30-1.4RANF30-2.0 in the X-band, respectively. (a 2-f 2) are impedance matching diagrams of RANF30RANF30-0.2RANF30-0.5RANF30-0.9RANF30-1.4RANF30-2.0 in the Ku band, respectively. In the Ku band, RANF30-0.9 has the most excellent impedance matching performance, which indicates that a large amount of electromagnetic waves enter the interior of the material, increasing the possibility of being attenuated.
Fig. 7 is a graph of attenuation constants of the polyaniline modified graphene composite wave-absorbing fiber fabrics obtained in examples 1 to 5, and it can be seen that the attenuation constants of the polyaniline hybrid RANF30 composite fabrics in the X (a) and K (b) bands are significantly better than those of the pure RANF30 composite fabrics, which indicates that the attenuation capability of the RANF30 composite fabrics to electromagnetic waves is stronger after hybridization of polyaniline. In the Ku band, the decay constant of RANF30-0.9 is not the best, but because of its best impedance matching properties, more electromagnetic waves enter the interior of the material, which is lost in the form of thermal energy, with the most excellent wave absorbing properties.
FIG. 8 is a Cole-Cole curve of the polyaniline-modified graphene composite wave-absorbing fiber fabric obtained in examples 1-5, wherein after polyaniline is grown in situ, the Cole-Cole curve has a plurality of semicircles, which illustrate interfacial polarization between RGO/ANF, RGO/RGO, RGO/air with various polarization mechanisms; residual oxygen-containing functional groups on the RGO surface, internal defects and dangling bonds can lead to dipole polarization and defect polarization caused by uneven distribution of surrounding electron clouds; the conductivity gradually increases with increasing concentration of the hydrochloric acid doped polyaniline due to the conductive loss caused by the long tail in the Cole-Cole curve, and the longer the tail in the Cole-Cole. In addition, the fibers in the fabric are mutually wound, electromagnetic waves conduct multiple times and scatter diffraction among the fibers, multiple loss is conducted, attenuation of the electromagnetic waves in the material is increased, and wave absorbing performance is facilitated.
The polyaniline modified graphene composite wave-absorbing fiber fabric prepared by the wet spinning technology is dried at room temperatureThe mechanical properties show that the fabric has excellent flexibility, achieves the mechanical properties required by braiding, and grows polyaniline doped with different hydrochloric acid concentrations on the surface of the RANF30 fabric in situ to improve the conductivity. The wave absorbing performance shows that in the Ku wave band, the frequency of the RANF30-0.9 is 12.8GHz at the thickness of 2.8mm, and the RL min -59.4dB, eab=4.9 GHz (12-16.9 GHz). Furthermore, when the thickness is 2.6mm, there is a maximum absorption bandwidth, the EAB thereof max =6 GHz (12-18 GHz), realizing complete coverage in the X and Ku bands, meeting the use requirements of "thin, light, wide and strong". The impedance matching and attenuation constant of the RANF30-0.9 composite fabric determine the wave absorbing performance, and the internal multiple loss mechanism increases the attenuation performance of electromagnetic waves.
Claims (10)
1. The preparation method of the polyaniline modified graphene composite wave-absorbing fiber fabric is characterized by comprising the following steps of:
step 1: mixing aramid fiber and alkali to prepare a solution, obtaining a dispersion liquid, and fully mixing and reacting to obtain aramid nanofiber;
step 2: preparing graphene oxide dispersion liquid;
step 3: mixing the aramid nanofiber obtained in the step 1 with graphene oxide dispersion liquid to obtain spinning stock solution, spinning into fibers by adopting a wet spinning method, braiding the fibers into fabrics, and reducing to obtain graphene aramid nanofiber composite fabrics; the mass ratio of the aramid nanofiber to the graphene oxide is as follows: 10:3;
step 4: adding an aniline monomer and the fabric obtained in the step 3 into an acid solution for soaking for T time, adding an ammonium persulfate solution for polymerization reaction, and cleaning and drying to obtain the polyaniline modified graphene composite wave-absorbing fiber fabric; wherein the mass ratio of the aniline monomer to the fabric in the step 3 is as follows: 10:1; the mass ratio of ammonium persulfate to aniline monomer is as follows: 1:1.
2. The preparation method of the polyaniline modified graphene composite wave-absorbing fiber fabric according to claim 1, wherein in the step 1, KOH is adopted as alkali, and the concentration of the aramid fiber in the dispersion liquid is 20mg/mL.
3. The preparation method of the polyaniline modified graphene composite wave-absorbing fiber fabric according to claim 1, wherein the concentration of graphene oxide in the graphene oxide dispersion liquid in the step 2 is 10mg/mL, and the size of graphene oxide sheets is 30-50 μm.
4. The preparation method of the polyaniline modified graphene composite wave-absorbing fiber fabric according to claim 1, wherein the coagulating liquid in the wet spinning in the step 3 is a mixed solution composed of hydrochloric acid and deionized water, and the volume ratio of the hydrochloric acid to the deionized water is 1:50; the extrusion speed of the spinning dope was 1mL/min, and the spin coagulation bath was 10r/min.
5. The method for preparing the polyaniline modified graphene composite wave-absorbing fiber fabric according to claim 1, wherein the reducing conditions in the step 3 are as follows: the hydroiodic acid was reduced at 40℃for 24 hours.
6. The preparation method of the polyaniline modified graphene composite wave-absorbing fiber fabric according to claim 1, wherein the soaking time of the aniline monomer and the fabric in the step 4 in an acid solution is 24 hours, the polymerization temperature is 0 ℃, and the reaction time is 6 hours.
7. The method for preparing the polyaniline modified graphene composite wave-absorbing fiber fabric according to claim 1, wherein the acid solution in the step 4 is hydrochloric acid aqueous solution.
8. The preparation method of the polyaniline modified graphene composite wave-absorbing fiber fabric according to claim 7, wherein the concentration of the hydrochloric acid aqueous solution is 0.2-2.0 mol/L.
9. The polyaniline modified graphene composite wave-absorbing fiber fabric obtained by any one of the preparation methods of claims 1-8, wherein polyaniline is tightly adhered to the surface of the graphene composite fiber fabric to form a compact polyaniline nano-layer; polyaniline has uniform particle size, particles are closely stacked and intertwined together in a rod-shaped structure to form a net-shaped structure.
10. The application of the polyaniline modified graphene composite wave-absorbing fiber fabric according to claim 9, wherein the polyaniline modified graphene composite fiber fabric is used for preparing the wave-absorbing fabric.
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