CN113912983B - Modified MXene/carbon fiber/epoxy resin composite material and preparation method thereof - Google Patents
Modified MXene/carbon fiber/epoxy resin composite material and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 107
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 72
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 230000005496 eutectics Effects 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000009832 plasma treatment Methods 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 6
- 235000019743 Choline chloride Nutrition 0.000 claims description 6
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 6
- 229960003178 choline chloride Drugs 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 230000008859 change Effects 0.000 description 9
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- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000013307 optical fiber Substances 0.000 description 1
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Abstract
The invention discloses a modified MXene/carbon fiber/epoxy resin composite material and a preparation method thereof, wherein the preparation method comprises the following steps: stirring the hydrogen bond acceptor, the acrylic acid and the imidazole at 60-90 ℃ for 0.5-1 h until the mixture becomes transparent, and filtering to obtain a eutectic solvent (DES); heating DES to 40-60 ℃, adding MXene, and intermittently performing ultrasonic treatment for 0.5-2 h to obtain modified MXene dispersion; and carrying out plasma treatment on the carbon fiber to obtain modified carbon fiber, immersing the modified carbon fiber in modified MXene dispersion liquid, then carrying out curing reaction under ultraviolet light to obtain a modified MXene/carbon fiber composite material, immersing the modified MXene/carbon fiber composite material in an epoxy resin and curing agent mixture, and carrying out curing molding under certain curing conditions to obtain the modified MXene/carbon fiber/epoxy resin composite material. The modified MXene/carbon fiber/epoxy resin composite material prepared by the invention has stronger conductivity and sensing performance.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a modified MXene/carbon fiber/epoxy resin composite material and a preparation method thereof.
Background
The carbon fiber/epoxy resin composite material is a high-performance composite material with high specific strength and specific modulus, is commonly used as a structural material, and has wide application in the fields of aerospace, automobiles, buildings and the like. In view of the bearing effect of the composite material, the structural damage of the composite material can bring great influence to the performance and safety of the whole structure in the use process, so that the real-time monitoring of the structural change in the use process is particularly important. The current common monitoring methods comprise ultrasonic monitoring, an optical fiber sensing system, a piezoresistance system and the like, wherein embedding the piezoresistance material into the composite material is one of the most efficient methods for realizing the self-sensing of the composite material at present, and when the composite material is deformed, the resistance in the material can be changed, so that the self-monitoring can be realized.
Transition metal carbide (MXene) is a novel two-dimensional inorganic compound in material science reported in 2011, and the chemical formula of MXene is M n+1 X n T x Wherein M is a transition metal (e.g., ti, V, nb, ta, cr, zr, etc.), X is C or N, and T is a surface group (e.g., -O, -F, OH, etc.). Ti (Ti) 3 C 2 T x The graphene-like material has high specific surface area, good thermal stability and excellent conductivity, and is always applied to the aspects of gas adsorption, sensors, lithium ion batteries, capacitors, catalysis, transparent conductive films and hydrogen storage materials. The filler with excellent conductivity such as MXene is added into the carbon fiber/epoxy resin composite material, and the filler is synergistic with a carbon fiber long Cheng Daodian network, so that the conductivity and the sensing performance of the carbon fiber/epoxy resin composite material can be improved, and the change rule of the electrical performance of the composite material can be observed under the stress effect, so that the self-perception of the health condition of the composite material can be realized. While the key to improving sensing performance is in three ways: 1) The conductivity of the filler; 2) Dispersibility of the filler; 3) And the interface acting force between the filler and the carbon fiber. Because MXene has high surface energy, the MXene is extremely easy to agglomerate, so that the sheets are difficult to separate, and the excellent performance of the MXene cannot be exerted. The problem of how to well disperse MXene and how to enhance the interfacial force between MXene and carbon fiber, thereby improving the self-perception capability of the carbon fiber/epoxy resin composite material is needed to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a modified MXene/carbon fiber/epoxy resin composite material and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of a modified MXene/carbon fiber/epoxy resin composite material comprises the following steps:
s1: preparation of the eutectic solvent (DES): stirring the hydrogen bond acceptor, the acrylic acid and the imidazole at 60-90 ℃ for 0.5-1 h until the mixture becomes transparent, and filtering to obtain a eutectic solvent (DES);
s2: modified MXene dispersion: heating the DES obtained in the step S1 to 40-60 ℃, adding MXene, and carrying out intermittent ultrasonic treatment for 0.5-2 h to obtain modified MXene dispersion;
s3: modified MXene and carbon fiber composite material: carrying out plasma treatment on the surface of the carbon fiber to obtain modified carbon fiber, then immersing the modified carbon fiber in the modified MXene dispersion liquid obtained in the step S2, and then carrying out curing reaction under the action of ultraviolet light to obtain a modified MXene// carbon fiber composite material;
s4: preparation of modified MXene/carbon fiber/epoxy resin composite material: and (3) dipping the modified MXene/carbon fiber composite material obtained in the step (S3) into a mixture of epoxy resin and a curing agent thereof, and curing and forming under a certain curing condition to obtain the modified MXene/carbon fiber/epoxy resin composite material.
Further, the mass ratio of the hydrogen bond acceptor, the acrylic acid and the imidazole in the S1 is 1 (1-5): 1-5.
Further, the hydrogen bond acceptor is selected from one of choline chloride, tetrabutylammonium chloride, tetramethylammonium chloride and dodecyltrimethylammonium chloride.
Further, the mass ratio of MXene to hydrogen bond acceptor is 0.5:1-2:1.
Further, intermittent ultrasound in S2 is performed, the ultrasound time is set to be 5min, and the intermittent time is set to be 5min, so that MXene can be fully dispersed in DES, and accumulation is avoided.
Further, the mass ratio of the carbon fiber to the MXene is 0.5:1-2:1.
Further, the plasma processing environment in S3 is: in the mixed gas of nitrogen and oxygen with the volume ratio of 95-98:2-5, the air pressure is 1.0Pa, the current is 1.0A, and the time is 15-30 min; the curing reaction conditions under ultraviolet light are as follows: the ultraviolet wavelength is 285nm, the power is 300W, and the irradiation time is 2-5 min. The MXene can be fully embedded into the crack at the contact point of the carbon fiber wires by plasma treatment and ultraviolet curing of the carbon fibers, so that the acting force between the MXene and the carbon fibers is improved.
Further, the epoxy resin in the S4 is E-51 epoxy resin, the curing agent is dicyandiamide, and the mass ratio of the carbon fiber to the epoxy resin is 3:100-20:100; the mass ratio of dicyandiamide to epoxy resin is 5:100.
Further, the certain curing conditions in S4 are: curing for 2-4 h at 150-160 ℃ and curing for 2-4 h at 180-190 ℃. Curing at different temperatures ensures that the epoxy resin is fully cured.
The invention aims to provide a modified MXene/carbon fiber/epoxy resin composite material prepared by the preparation method of the modified MXene/carbon fiber/epoxy resin composite material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The conductivity of the MXene is high, and the addition of the MXene can enhance the conductivity of the carbon fiber, so that the carbon fiber forms a more perfect conductive network structure, and the conductivity and the sensing performance of the composite material are enhanced.
(2) Because the DES has good solubility and dispersibility and good conductivity, the MXene can be uniformly dispersed in the DES, so that the agglomeration of the MXene is avoided, the sheet layers of the DES are better separated, and the strong conductivity of the DES is exerted.
(3) Selecting a DES system containing acrylic acid, and under the action of ultraviolet light, carrying out a curing reaction on the DES system and the modified carbon fiber after plasma treatment, so that the interface action between the modified MXene and the carbon fiber can be enhanced; selecting a DES system containing imidazole, which can react with the epoxy resin, so that the interface effect between MXene and the epoxy resin is improved; thereby improving the sensing performance of the composite material.
(4) The MXene is embedded into the cracks of the carbon fiber wires at the contact points, and the unique layered structure of the MXene is utilized to enhance the structural perception sensitivity of the composite material.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the following will briefly explain the embodiments or drawings that are required to be used in the description of the prior art.
FIG. 1 is a flow chart of a method for preparing a modified MXene/carbon fiber/epoxy resin composite.
FIG. 2 is a graph showing the linear fit of the change in resistance (. DELTA.R/R0) versus tensile strain for the modified MXene/carbon fiber/epoxy composites prepared in examples (1, 2, 3, 4) and comparative examples (1, 2) of the present invention.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
As shown in fig. 1, the preparation method of the modified MXene/carbon fiber/epoxy resin composite material according to an embodiment includes the following steps:
s1: preparation of the eutectic solvent (DES): stirring the hydrogen bond acceptor, the acrylic acid and the imidazole at 60-90 ℃ for 0.5-1 h until the mixture becomes transparent, and filtering to obtain the eutectic solvent (DES).
Wherein the mass ratio of the hydrogen bond acceptor to the acrylic acid to the imidazole in the S1 is 1 (1-5); the hydrogen bond acceptor is selected from one of choline chloride, tetrabutylammonium chloride, tetramethyl ammonium chloride and dodecyl trimethyl ammonium chloride.
S2: modified MXene dispersion: heating the DES obtained in the step S1 to 40-60 ℃, adding MXene, and carrying out intermittent ultrasonic treatment for 0.5-2 h to obtain the modified MXene dispersion liquid.
Wherein the mass ratio of MXene to hydrogen bond acceptor is 0.5:1-2:1. Preferably, the parameter of intermittent ultrasound can be specifically set to 5min for intermittent time of 5min.
S3: modified MXene and carbon fiber composite material: and (3) carrying out plasma treatment on the surface of the carbon fiber to obtain modified carbon fiber, then immersing the modified carbon fiber in the modified MXene dispersion liquid obtained in the step (S2), and then carrying out curing reaction under the action of ultraviolet light to modify the MXene/carbon fiber composite material.
Wherein the mass ratio of the carbon fiber to the MXene is 0.5:1-2:1. Preferably, parameters of the plasma processing environment may be specifically set as follows: in the mixed gas of nitrogen and oxygen with the volume ratio of 95-98:2-5, the air pressure is 1.0Pa, the current is 1.0A, and the time is 15-30 min;
preferably, the parameters of the curing reaction under ultraviolet light can be specifically set as follows: the wavelength of ultraviolet light is 285nm, the power is 300W, and the irradiation time is 2-5 min.
S4: preparation of modified MXene/carbon fiber/epoxy resin composite material: and (3) dipping the modified MXene/carbon fiber composite material obtained in the step (S3) into a mixture of epoxy resin and a curing agent thereof, and curing and forming under a certain curing condition to obtain the modified MXene/carbon fiber/epoxy resin composite material.
Wherein the epoxy resin is E-51 epoxy resin, the curing agent is dicyandiamide, and the mass ratio of the carbon fiber to the epoxy resin is 3:100-20:100; the mass ratio of dicyandiamide to epoxy resin is 5:100. Preferably, specific parameters can be set for a certain curing condition: curing for 2-4 h at 150-160 ℃ and curing for 2-4 h at 180-190 ℃.
The following are the specific examples section:
example 1
1. Preparation of the eutectic solvent (DES): 80 parts by mass of choline chloride, 80 parts by mass of acrylic acid, and 80 parts by mass of imidazole were charged into a three-necked flask. Stirring at 90℃for 1h until the mixture became transparent, and filtering to give the eutectic solvent (DES).
2. Preparation of modified MXene Dispersion: heating DES to 40 ℃, adding 40 parts by mass of MXene, and carrying out intermittent ultrasonic treatment for 2 hours, wherein the ultrasonic time is set to be 5 minutes, and the intermittent time is set to be 5 minutes, so as to obtain modified MXene dispersion liquid;
3. preparation of a modified MXene and carbon fiber composite material: carrying out plasma treatment on 20 parts by mass of carbon fibers for 15min under the conditions that the air pressure is 1.0Pa and the current is 1.0A in a mixed gas of nitrogen and oxygen in a volume ratio of 95:5 to obtain modified carbon fibers; then dipping the material into modified MXene dispersion liquid, and then irradiating the material for 2 minutes under ultraviolet light with the wavelength of 285nm and the power of 300W, and carrying out curing reaction to obtain a modified MXene/carbon fiber composite material;
4. preparation of modified MXene/carbon fiber/epoxy resin composite material: the modified MXene/carbon fiber composite material is immersed in a mixture of 100 parts by mass of E-51 epoxy resin and 5 parts by mass of dicyandiamide curing agent, and is cured for 2 hours at 150 ℃ and 2 hours at 180 ℃ to obtain the modified MXene/carbon fiber/epoxy resin composite material.
Example 2
1. Preparation of the eutectic solvent (DES): 15 parts by mass of tetrabutylammonium chloride, 30 parts by mass of acrylic acid, 30 parts by mass of imidazole were added to a three-necked flask, and stirred at 80℃for 1 hour until the mixture became transparent, and filtered to obtain a eutectic solvent (DES).
2. Preparation of modified MXene Dispersion: heating DES to 50 ℃, adding 15 parts by mass of MXene, and carrying out intermittent ultrasonic treatment for 1.5 hours, wherein the ultrasonic time is set to be 5 minutes, and the intermittent time is set to be 5 minutes, so as to obtain modified MXene dispersion liquid;
3. preparation of a modified MXene and carbon fiber composite material: carrying out plasma treatment on 15 parts by mass of carbon fibers for 20min under the conditions of air pressure of 1.0Pa and current of 1.0A in a mixed gas of nitrogen and oxygen with a volume ratio of 96:4 to obtain modified carbon fibers, immersing the modified carbon fibers in a modified MXene dispersion liquid, irradiating for 3 min under ultraviolet light with a wavelength of 285nm and a power of 300W, and carrying out curing reaction to obtain a modified MXene/carbon fiber composite material;
4. preparation of modified MXene/carbon fiber/epoxy resin composite material: the modified MXene/carbon fiber composite material is immersed in a mixture of 100 parts by mass of E-51 epoxy resin and 5 parts by mass of dicyandiamide curing agent, and is cured for 3 hours at 150 ℃ and 3 hours at 180 ℃ to obtain the modified MXene/carbon fiber/epoxy resin composite material.
Example 3
1. Preparation of the eutectic solvent (DES): 4 parts by mass of choline chloride, 8 parts by mass of acrylic acid, and 20 parts by mass of imidazole were added to a three-necked flask, and the mixture was stirred at 70 ℃ for 1 hour until the mixture became transparent, and filtered to obtain a eutectic solvent (DES).
2. Preparation of modified MXene Dispersion: heating DES to 40 ℃, adding 6 parts by mass of MXene, and carrying out intermittent ultrasonic treatment for 1h, wherein the ultrasonic time is set to be 5min, and the intermittent time is set to be 5min, so as to obtain modified MXene dispersion liquid;
3. preparation of a modified MXene and carbon fiber composite material: carrying out plasma treatment on 9 parts by mass of carbon fibers for 20min under the conditions of air pressure of 1.0Pa and current of 1.0A in a mixed gas of nitrogen and oxygen in a volume ratio of 97:3 to obtain modified carbon fibers, immersing the modified carbon fibers in a modified MXene dispersion liquid, irradiating for 4 min under ultraviolet light with a wavelength of 285nm and a power of 300W, and carrying out curing reaction to obtain a modified MXene/carbon fiber composite material;
4. preparation of modified MXene/carbon fiber/epoxy resin composite material: the modified MXene/carbon fiber composite material is immersed in a mixture of 100 parts by mass of E-51 epoxy resin and 5 parts by mass of dicyandiamide curing agent, and is cured for 2 hours at 160 ℃ and 2 hours at 190 ℃ to obtain the modified MXene/carbon fiber/epoxy resin composite material.
Example 4
1. Preparation of the eutectic solvent (DES): 0.75 parts by mass of choline chloride, 3.75 parts by mass of acrylic acid, and 3.75 parts by mass of imidazole were charged into a three-necked flask. Stirring at 60℃for 1h until the mixture became transparent, and filtering to give the eutectic solvent (DES).
2. Preparation of modified MXene Dispersion: heating DES to 60 ℃, adding 1.5 parts by mass of MXene, and carrying out intermittent ultrasonic treatment for 0.5h, wherein the ultrasonic time is set to be 5min, and the intermittent time is set to be 5min, so as to obtain modified MXene dispersion liquid;
3. preparation of a modified MXene and carbon fiber composite material: 3 parts by mass of carbon fiber is subjected to plasma treatment for 30min under the conditions of the air pressure of 1.0Pa and the current of 1.0A in a mixed gas of nitrogen and oxygen with the volume ratio of 98:2 to obtain modified carbon fiber, then the modified carbon fiber is immersed in modified MXene dispersion liquid, and then irradiated for 5min under ultraviolet light with the wavelength of 285nm and the power of 300W, and the modified MXene/carbon fiber composite material is obtained through curing reaction;
4. preparation of modified MXene/carbon fiber/epoxy resin composite material: the modified MXene/carbon fiber composite material is immersed in a mixture of 100 parts by mass of E-51 epoxy resin and 5 parts by mass of dicyandiamide curing agent, and is cured for 4 hours at 160 ℃ and for 4 hours at 190 ℃ to obtain the modified MXene/carbon fiber/epoxy resin composite material.
Comparative example 1
40 parts by mass of MXene, 20 parts by mass of carbon fiber and 100 parts by mass of E-51 epoxy resin which are not subjected to DES treatment are subjected to intermittent ultrasonic treatment for 2 hours, wherein the ultrasonic time is set to be 5 minutes, and the intermittent time is set to be 5 minutes; then adding 5 parts by mass of dicyandiamide curing agent, curing for 2 hours at 150 ℃ and curing for 2 hours at 180 ℃ to obtain the MXene/carbon fiber/epoxy resin composite material.
Comparative example 2
Intermittently performing ultrasonic treatment on 6 parts by mass of MXene, 9 parts by mass of carbon fiber and 100 parts by mass of E-51 epoxy resin which are not subjected to DES treatment for 1h, wherein the ultrasonic time is set to be 5min, and the intermittent time is set to be 5min; then adding 5 parts by mass of dicyandiamide curing agent, curing for 2 hours at 160 ℃ and curing for 2 hours at 190 ℃ to obtain the MXene/carbon fiber/epoxy resin composite material.
Comparative example 3
Intermittently performing ultrasonic treatment on 1.5 parts by mass of MXene, 23 parts by mass of carbon fiber and 100 parts by mass of E-51 epoxy resin which are not subjected to DES treatment for 0.5 hour, wherein the ultrasonic time is set to be 5 minutes, and the intermittent time is set to be 5 minutes; then adding 5 parts by mass of dicyandiamide curing agent, curing for 4 hours at 160 ℃ and curing for 4 hours at 190 ℃ to obtain the MXene/carbon fiber/epoxy resin composite material.
Test conditions
1. Mechanical property test: according to GB/T2567-2008 test standard, the tensile strength and the bending strength of the modified MXene/carbon fiber/epoxy resin composite material test strip are measured on a universal mechanical testing machine respectively. At least 3 replicates per group were tested and the results averaged.
2. Resistivity test: the graphene/epoxy composite was resistivity tested using a digital high resistance meter, standard GB/T1410-2006. At least 5 random positions were tested for each group and the results averaged.
3. Strain sensitivity test: after applying a fixed voltage of 3V to the modified MXene/carbon fiber/epoxy composite spline through a wire using a digital instrument, the relative resistance change (Δrjr0) with the change in tensile strain of the modified MXene/carbon fiber/epoxy composite was measured. The relative resistance change (ΔR/R0) is calculated as follows: Δr/r0= (R-R0)/R0
Wherein R0 and R are the resistance in the absence of strain and the resistance when strain is applied, respectively. The relation between the relative resistance change (delta R/R0) and the tensile strain is analyzed and is subjected to linear fitting, and the obtained linear slope is the strain sensing sensitivity factor (GF).
As shown in fig. 2, the values of the modified MXene/carbon fiber/epoxy strain sensing sensitivity factor (GF) can be obtained by linear fitting the relationship of the relative resistance change to the tensile strain shown in the analysis chart and are filled in table 2. Since comparative example 3 is an insulator, the resistance R0 cannot be measured, and therefore, the resistance change (Δr/R0) cannot be calculated, and the strain sensing factor (GF) cannot be obtained.
Table 1 composite material respective component types and mass distribution tables of examples and comparative examples
| Sample of | DES (Hydrogen bond acceptor: acrylic acid: imidazole) | MXene | Carbon fiber | Epoxy resin | Dicyandiamide |
| Example 1 | 80:80:80 | 40 | 20 | 100 | 5 |
| Example 2 | 15:30:30 | 15 | 15 | 100 | 5 |
| Example 3 | 4:8:20 | 6 | 9 | 100 | 5 |
| Example 4 | 0.75:3.75:3.75 | 1.5 | 3 | 100 | 5 |
| Comparative example 1 | 0 | 40 | 20 | 100 | 5 |
| Comparative example 2 | 0 | 6 | 9 | 100 | 5 |
| Comparative example 3 | 0 | 1.5 | 3 | 100 | 5 |
Table 2 mechanical properties, resistivity and strain sensing sensitivity factors of the composites of examples and comparative examples
The types and mass distribution of the components of the composite materials of the examples and the comparative examples are shown in table 1, and the mechanical properties, the resistivity and the strain sensing sensitivity factors of the composite materials of the examples and the comparative examples are shown in table 2.
As can be seen from the data of examples 1 and 1, 3 and 2, and 4 and 3 in tables 1 and 2, the DES modified MXene/carbon fiber/epoxy composite material, while having both MXene and carbon fiber contents, has significantly higher tensile strength, flexural strength and strain sensing sensitivity (GF) than the untreated comparative example and significantly lower electrical resistivity than the untreated comparative example. This is mainly due to the following aspects: 1) Because the selected DES system has good dispersing and dissolving performance, the MXene and the carbon fiber are uniformly dispersed; 2) Acrylic acid and imidazole in DES are helpful for improving interface effect of MXene, carbon fiber and epoxy resin, so that sensing performance of the composite material is improved. (3) The MXene with good dispersity is embedded into the crack of the contact points of the carbon fiber wires, and the unique layered structure of the MXene is utilized to enhance the sensitivity of the structural perception of the composite material.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the modified MXene/carbon fiber/epoxy resin composite material is characterized by comprising the following steps:
s1: preparation of the eutectic solvent (DES): stirring the hydrogen bond acceptor, the acrylic acid and the imidazole at 60-90 ℃ for 0.5-1 h until the mixture becomes transparent, and filtering to obtain a eutectic solvent (DES);
s2: modified MXene dispersion: heating the DES obtained in the step S1 to 40-60 ℃, adding MXene, and carrying out intermittent ultrasonic treatment for 0.5-2 h to obtain modified MXene dispersion;
s3: modified MXene and carbon fiber composite material: carrying out plasma treatment on the surface of the carbon fiber to obtain modified carbon fiber, then dipping the modified carbon fiber in the modified MXene dispersion liquid obtained in the step S2, and then carrying out curing reaction under the action of ultraviolet light to obtain a modified MXene/carbon fiber composite material;
s4: preparation of modified MXene/carbon fiber/epoxy resin composite material: and (3) dipping the modified MXene/carbon fiber composite material obtained in the step (S3) into a mixture of epoxy resin and a curing agent thereof, and curing and forming under a certain curing condition to obtain the modified MXene/carbon fiber/epoxy resin composite material.
2. The preparation method of the modified MXene/carbon fiber/epoxy resin composite material according to claim 1, wherein the mass ratio of the hydrogen bond acceptor to the acrylic acid to the imidazole in the S1 is 1 (1-5): 1-5.
3. The method for preparing the modified MXene/carbon fiber/epoxy resin composite material according to claim 2, wherein the hydrogen bond acceptor is one selected from choline chloride, tetrabutylammonium chloride, tetramethyl ammonium chloride and dodecyl trimethyl ammonium chloride.
4. The method for preparing the modified MXene/carbon fiber/epoxy resin composite material according to claim 1, wherein the mass ratio of the MXene to the hydrogen bond acceptor is 0.5:1-2:1.
5. The method for preparing the modified MXene/carbon fiber/epoxy resin composite material according to claim 1, wherein the intermittent ultrasound in the step S2 is set to be 5min, and the intermittent time is set to be 5min.
6. The method for preparing the modified MXene/carbon fiber/epoxy resin composite material according to claim 1, wherein the mass ratio of the carbon fiber to the MXene is 0.5:1-2:1.
7. The method for preparing a modified MXene/carbon fiber/epoxy resin composite material according to claim 1, characterized in that the plasma treatment environment in S3 is: in the mixed gas of nitrogen and oxygen with the volume ratio of (95-98) to (2-5), the air pressure is 1.0Pa, the current is 1.0A, and the time is 15-30; the curing reaction conditions under ultraviolet light are as follows: the ultraviolet wavelength is 285nm, the power is 300W, and the irradiation time is 2-5 minutes.
8. The preparation method of the modified MXene/carbon fiber/epoxy resin composite material according to claim 1, wherein the epoxy resin in the S4 is E-51 epoxy resin, the curing agent is dicyandiamide, and the mass ratio of the carbon fiber to the epoxy resin is 3:100-20:100; the mass ratio of dicyandiamide to epoxy resin is 5:100.
9. The method for preparing a modified MXene/carbon fiber/epoxy resin composite material according to claim 1, characterized in that the certain curing condition in S4 is: curing for 2-4 h at 150-160 ℃ and curing for 2-4 h at 180-190 ℃.
10. A modified MXene/carbon fiber/epoxy resin composite material prepared according to the method of any one of claims 1 to 9.
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