CN115710406A - Preparation method and application of electromagnetic shielding carbon fiber fabric composite material based on reduced graphene oxide reinforcement - Google Patents
Preparation method and application of electromagnetic shielding carbon fiber fabric composite material based on reduced graphene oxide reinforcement Download PDFInfo
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- CN115710406A CN115710406A CN202211363397.1A CN202211363397A CN115710406A CN 115710406 A CN115710406 A CN 115710406A CN 202211363397 A CN202211363397 A CN 202211363397A CN 115710406 A CN115710406 A CN 115710406A
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- electromagnetic shielding
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 69
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000004744 fabric Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000002787 reinforcement Effects 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 229920006253 high performance fiber Polymers 0.000 claims description 4
- 230000002265 prevention Effects 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000001721 transfer moulding Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000009941 weaving Methods 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 7
- QZAYGJVTTNCVMB-UHFFFAOYSA-N serotonin Chemical class C1=C(O)C=C2C(CCN)=CNC2=C1 QZAYGJVTTNCVMB-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
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- 238000012986 modification Methods 0.000 description 1
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- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a preparation method and application of a reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material. The electromagnetic shielding carbon fiber fabric composite material has the advantages of simple process, low production cost, stable function, good scientific value and benefit prospect, multiple purposes and wide market application prospect.
Description
Technical Field
The invention belongs to the technical field of functional composite materials, and particularly relates to a preparation method and application of an electromagnetic shielding carbon fiber fabric composite material based on reduced graphene oxide reinforcement.
Background
Modern informatization has been rapidly developed, and electromagnetic waves have become a resource widely used in electronic devices. With the application of electromagnetic waves, the electromagnetic interference has increasingly more and more influence on electronic products, which is a serious hazard for equipment, systems and ecology. There are strict limitations on the electromagnetic interference (EMI) of electronic and electromagnetic instruments in different countries, wherein electromagnetic shielding is a method of controlling the propagation induction of electromagnetic waves from one area to another by means of isolation. The electromagnetic shielding performance of the pure carbon fiber composite material is not high and the application performance is greatly limited.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of a reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material, so as to solve the problems of low electromagnetic shielding performance and limited application of the existing carbon fiber composite material.
The first object of the present invention can be achieved by the following technical solutions: a preparation method of a reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material comprises the following steps: selecting a carbon fiber fabric as a base material, coating the graphene oxide aqueous solution on the surface of the base material, then solidifying the graphene oxide aqueous solution, reducing the graphene oxide in the surface of the carbon fiber fabric by using water and hydrazine, and finally preparing the reduced sample into the electromagnetic shielding carbon fiber fabric composite material by using a VARTM (vacuum transfer molding) process. The electromagnetic shielding carbon fiber fabric composite material prepared by the method has good electromagnetic shielding performance.
Preferably, the aqueous graphene oxide solution is coated on the substrate at least once.
Preferably, the graphene oxide is prepared by a modified Hummers method, the graphene oxide is prepared into a 0.05-10mg/ml graphene oxide aqueous solution, and the graphene oxide aqueous solution is subjected to ultrasonic treatment for 15-120 minutes by an ultrasonic machine.
Preferably, the method further comprises the step of pressing out the excessive graphene oxide solution in the coated substrate by pressure, wherein the pressure value is 50-100kg.
Preferably, the step of VARTM process curing molding specifically includes: sealing and vacuum treating the resin at-0.01 to-0.1 MPa for 0.5 to 2 hours; then injecting epoxy resin containing 30% -50% of modified anhydride with vacuum assistance, and curing in 3 stages to prepare the composite material plate.
Preferably, the 3 stages are respectively: curing for 2 hours at the temperature of less than or equal to 90 ℃; curing for 4 hours at the temperature of less than or equal to 110 ℃, and curing for 1 hour at the temperature of less than or equal to 130 ℃.
Preferably, the carbon fiber fabric is formed by blending carbon fiber materials and high-performance fibers, wherein the high-performance fibers include but are not limited to one or more blends of aramid fibers, glass fibers, wholly aromatic polyester fibers or high-strength polyethylene fibers.
Preferably, the carbon fiber fabric is textured including, but not limited to, woven or knitted.
Preferably, the carbon fiber fabric is carbon fiber woven cloth; the thickness interval is 1-6 layers. The thickness of different carbon fiber fabrics is controlled, and carbon fiber composite materials with different electromagnetic shielding effects can be realized.
According to another aspect of the invention, the application of the reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material is characterized in that the reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material prepared by the method is applied to military lightning protection radomes and electromagnetic interference prevention covers of precision instruments.
Compared with the prior art, the invention has the following advantages:
(1) Provides a novel preparation method of a modified carbon fiber composite material with enhanced electromagnetic shielding effect.
(2) The composite material is realized by a VARTM process, has low production cost, various and stable functions and good benefit prospect, and is beneficial to the composite materials such as special military composite materials for military use, such as radar prevention, precision instrument discharge magnetic interference and the like.
(3) The composite material can realize reliable control of electromagnetic shielding performance through coating amount and the thickness of the carbon fiber base material.
Drawings
Fig. 1 is a schematic process flow diagram of a preparation method of a reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material according to an embodiment of the invention.
Fig. 2 is a graph comparing the electromagnetic shielding performance of the electromagnetically shielded carbon fiber fabric composite (RGO) of the embodiment of the present invention with that of the pure carbon fiber Composite (CF) under different thickness conditions.
Fig. 3 is a graph of data of electrothermal effect of the electromagnetic shielding carbon fiber fabric composite material prepared by the method in the embodiment under different current conditions.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Example 1
As shown in fig. 1, the preparation method of the electromagnetic shielding carbon fiber fabric composite material based on reduced graphene oxide reinforcement provided by the invention comprises the following steps:
step 1: preparing 6mg/ml graphene oxide aqueous solution from graphene oxide prepared by an improved Hummers method, and directly coating the graphene oxide aqueous solution on the surface of a carbon fiber fabric after ultrasonic treatment for 30 minutes;
and 2, step: pressing the coated carbon fiber substrate out of redundant graphene oxide aqueous solution by using 50kg of pressure, putting the coated carbon fiber substrate into an oven, controlling the vacuum degree to be-0.09 MPa by using a vacuum pump so as to eliminate air bubbles in a fabric tissue, and then drying the coated carbon fiber substrate in the oven at 50 ℃ for 6 hours to solidify the graphene oxide;
and 3, step 3: reducing the graphene oxide on the surface of the coated carbon fiber substrate into reduced graphene oxide by using hydrazine hydrate;
and 4, step 4: mixing epoxy resin, modified anhydride and 5-hydroxytryptamine in a mass ratio of 100:85:2 mixing to prepare an epoxy resin combined solution, preheating the epoxy resin combined solution for half an hour at 60 ℃, then placing the epoxy resin composition in a vacuum oven for 30 minutes at 60 ℃, and controlling the vacuum degree to be-0.09 MPa by using a vacuum pump so as to eliminate bubbles in the resin composition;
and 5: the composite unit is made using a VARTM process, which takes approximately 3 hours. There were 3 additional stages of curing: curing for 2 hours at the temperature of 70 ℃; curing for 4 hours at the temperature of 105 ℃, curing for 1 hour at the temperature of 115 ℃ and finally preparing the composite material plate.
The electromagnetic shielding carbon fiber fabric composite material prepared by the steps has good electrothermal effect, as shown in figure 3. The results of comparing the electromagnetic shielding performance of the composite material with that of a pure carbon fiber composite material prepared from pure carbon fibers are shown in fig. 2, and the experimental composite material is obviously better than the pure carbon fiber composite material in electromagnetic shielding performance under the actual measurement of different thicknesses.
Example 2
Referring to fig. 1, the specific steps of this embodiment are as follows:
step 1: preparing graphene oxide prepared by an improved Hummers method into a 1mg/ml graphene oxide aqueous solution, and directly coating the graphene oxide aqueous solution on the surface of a carbon fiber fabric after ultrasonic treatment for 50 minutes;
and 2, step: pressing the coated carbon fiber substrate out of redundant graphene oxide aqueous solution by using 30kg of pressure, putting the coated carbon fiber substrate into a drying oven, controlling the vacuum degree to be-0.09 MPa by using a vacuum pump so as to eliminate bubbles in a fabric tissue, and then putting the coated carbon fiber substrate into the drying oven to dry for 6 hours at 60 ℃ so as to solidify the graphene oxide;
and step 3: reducing the graphene oxide on the surface of the coated carbon fiber substrate into reduced graphene oxide by using hydrazine hydrate;
and 4, step 4: mixing epoxy resin, modified anhydride and 5-hydroxytryptamine in a mass ratio of 100:85:2 mixing to prepare an epoxy resin combined solution, preheating the epoxy resin combined solution for half an hour at the temperature of 60 ℃, then placing the epoxy resin composition in a vacuum oven for 1 hour at the temperature of 60 ℃, and controlling the vacuum degree to be-0.09 MPa by a vacuum pump so as to eliminate air bubbles in the resin composition;
and 5: the composite unit is made using a VARTM process, which takes approximately 3 hours. Curing was carried out in 3 stages: curing for 2 hours at the temperature of 80 ℃; curing for 4 hours at the temperature of 100 ℃, and curing for 1 hour at the temperature of 130 ℃ to finally obtain the composite material plate.
Example 3
Referring to fig. 1, the specific steps of this embodiment are as follows:
step 1: preparing 7mg/ml graphene oxide aqueous solution from graphene oxide prepared by an improved Hummers method, and directly coating the graphene oxide aqueous solution on the surface of a carbon fiber fabric after ultrasonic treatment for 80 minutes;
step 2: pressing the coated carbon fiber substrate out of redundant graphene oxide aqueous solution by using 50kg of pressure, putting the coated carbon fiber substrate into an oven, controlling the vacuum degree to be-0.09 MPa by using a vacuum pump so as to eliminate bubbles in a fabric tissue, and then drying the coated carbon fiber substrate in the oven at 60 ℃ for 6 hours to solidify the graphene oxide;
and step 3: reducing the graphene oxide on the surface of the coated carbon fiber substrate into reduced graphene oxide by using hydrazine hydrate;
and 4, step 4: mixing epoxy resin, modified anhydride and 5-hydroxytryptamine in a mass ratio of 100:85:2 mixing to prepare an epoxy resin combined solution, preheating the epoxy resin combined solution for half an hour at the temperature of 60 ℃, then placing the epoxy resin composition in a vacuum oven for 1.5 hours at the temperature of 60 ℃, and controlling the vacuum degree to be-0.09 MPa by a vacuum pump so as to eliminate air bubbles in the resin composition;
and 5: the composite unit is made using a VARTM process, which takes approximately 3 hours. There were 3 additional stages of curing: curing for 2 hours at the temperature of 75 ℃; curing for 4 hours at the temperature of 110 ℃, curing for 1 hour at the temperature of 130 ℃ and finally preparing the composite material plate.
The product prepared by the method can be applied to special military articles such as military lightning-proof antenna covers, electromagnetic interference prevention cover bodies of precise instruments and the like, has good electromagnetic shielding effect, and particularly has the highest shielding performance of 95dB and excellent performance under the thickness of 4 mm.
In addition, the method can also directly use fibers, yarns and the like as a base material, coat graphene oxide on the surface of the base material, reduce the graphene oxide to obtain the fibers, yarns and the like coated with reduced graphene oxide, and then process the fibers, yarns and the like into fabrics.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments, or alternatives may be employed, by those skilled in the art, without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of an electromagnetic shielding carbon fiber fabric composite material based on reduced graphene oxide reinforcement is characterized by comprising the following steps: selecting a carbon fiber fabric as a substrate, coating the surface of the substrate with a graphene oxide aqueous solution, solidifying the substrate, reducing the graphene oxide on the surface of the carbon fiber fabric by using water and hydrazine, and finally preparing the reduced sample into the electromagnetic shielding carbon fiber fabric composite material by using a VARTM (vacuum assisted transfer molding) process. The electromagnetic shielding carbon fiber fabric composite material prepared by the method has good electromagnetic shielding performance.
2. The preparation method of the reduced graphene oxide reinforced electromagnetic shielding-based carbon fiber fabric composite material based on claim 1, wherein the graphene oxide aqueous solution is coated on the substrate at least once.
3. The preparation method of the reduced graphene oxide reinforced electromagnetic shielding-based carbon fiber fabric composite material as claimed in claim 2, wherein the graphene oxide is prepared by a modified Hummers method, and the graphene oxide is prepared into 0.05-10mg/ml graphene oxide aqueous solution, and is subjected to ultrasonic treatment for 15-120 minutes by an ultrasonic machine.
4. The preparation method of the reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material according to claim 1, 2 or 3, further comprising the step of pressing out the excessive graphene oxide solution in the coated substrate by pressure, wherein the pressure value is 50-100kg.
5. The preparation method of the reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material according to claim 1, 2 or 3, wherein the step of performing curing molding by the VARTM process specifically comprises: sealing and vacuum treating the resin at-0.01 to-0.1 MPa for 0.5 to 2 hours; then injecting epoxy resin containing 30% -50% of modified anhydride with vacuum assistance, and curing in 3 stages to prepare the composite material plate.
6. The preparation method of the electromagnetic shielding carbon fiber fabric composite material based on the reduced graphene oxide reinforcement, which is characterized in that the 3 stages are respectively as follows: curing for 2 hours at the temperature of less than or equal to 90 ℃; curing for 4 hours at the temperature of less than or equal to 110 ℃, and curing for 1 hour at the temperature of less than or equal to 130 ℃.
7. The preparation method of the reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material as claimed in claim 1, 2 or 3, wherein the carbon fiber fabric is formed by co-weaving a carbon fiber material and high-performance fibers, and the high-performance fibers include but are not limited to one or more of aramid fibers, glass fibers, wholly aromatic polyester fibers or high-strength polyethylene fibers.
8. The preparation method of the reduced graphene oxide reinforced electromagnetic shielding-based carbon fiber fabric composite material as claimed in claim 7, wherein the carbon fiber fabric is woven, but not limited to, woven or knitted.
9. The preparation method of the electromagnetic shielding carbon fiber fabric composite material based on the reduced graphene oxide reinforcement is characterized in that the carbon fiber fabric is a carbon fiber woven fabric; the thickness interval is 1-6 layers. The thickness of different carbon fiber fabrics is controlled, and carbon fiber composite materials with different electromagnetic shielding effects can be realized.
10. The application of the reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material is characterized in that the reduced graphene oxide reinforced electromagnetic shielding carbon fiber fabric composite material prepared by the method according to any one of claims 1 to 9 is applied to military radar-proof antenna covers and electromagnetic interference prevention covers of precision instruments.
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| CN202211363397.1A CN115710406A (en) | 2022-11-02 | 2022-11-02 | Preparation method and application of electromagnetic shielding carbon fiber fabric composite material based on reduced graphene oxide reinforcement |
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| CN202211363397.1A CN115710406A (en) | 2022-11-02 | 2022-11-02 | Preparation method and application of electromagnetic shielding carbon fiber fabric composite material based on reduced graphene oxide reinforcement |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514564A (en) * | 2023-04-28 | 2023-08-01 | 上海大学 | Graphene oxide modified carbon/carbon composite material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514564A (en) * | 2023-04-28 | 2023-08-01 | 上海大学 | Graphene oxide modified carbon/carbon composite material and preparation method thereof |
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Application publication date: 20230224 |