CN109207970B - Carbon fiber cloth-nano copper composite material and preparation method and application thereof - Google Patents
Carbon fiber cloth-nano copper composite material and preparation method and application thereof Download PDFInfo
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- CN109207970B CN109207970B CN201811285329.1A CN201811285329A CN109207970B CN 109207970 B CN109207970 B CN 109207970B CN 201811285329 A CN201811285329 A CN 201811285329A CN 109207970 B CN109207970 B CN 109207970B
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 92
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 92
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000010949 copper Substances 0.000 title claims abstract description 68
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 66
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004744 fabric Substances 0.000 claims abstract description 52
- 238000005507 spraying Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- 238000002791 soaking Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 14
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 14
- 238000007788 roughening Methods 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 12
- 206010070834 Sensitisation Diseases 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 230000008313 sensitization Effects 0.000 claims description 10
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 7
- 239000001119 stannous chloride Substances 0.000 claims description 7
- 235000011150 stannous chloride Nutrition 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 229920002120 photoresistant polymer Polymers 0.000 claims description 6
- 230000001235 sensitizing effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000005452 bending Methods 0.000 abstract description 2
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000007747 plating Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 8
- 238000000861 blow drying Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001476 sodium potassium tartrate Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention belongs to the field of composite materials, and discloses a carbon fiber cloth-nano copper composite material, and a preparation method and application thereof. And (3) pretreating the carbon fiber cloth, spraying a copper-containing solution and a reducing solution on the surface of the pretreated carbon fiber cloth, and drying to obtain the carbon fiber cloth-nano copper composite material. The preparation method for spraying the nano-copper on the surface of the carbon fiber cloth has simple process, is easy to realize, has low cost compared with the traditional carbon fiber chemical copper plating or magnetron sputtering process, and is suitable for batch production. The obtained carbon fiber cloth-nano copper composite material has excellent wave-absorbing performance, uniform copper coating, good conductivity and good bending resistance. Meanwhile, the defects of poor flexibility, heavy weight, high production cost, easy corrosion and the like of the traditional metal material are overcome. Can be used as electromagnetic shielding material with excellent performance.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a carbon fiber cloth-nano copper composite material as well as a preparation method and application thereof.
Background
With the rapid development of science and technology, internet +, artificial intelligence and big data relate to all the fields of society. The flexible electronic, wearable equipment and the implanted biomedical system are widely applied, so that on one hand, a great deal of convenience is brought to the life of human beings; on the other hand, as the use of electronic devices and systems is increased, the electromagnetic radiation amount of electromagnetic waves is increased rapidly, which brings a series of social problems and environmental problems, such as electromagnetic interference, leakage of electromagnetic information, and harm of electromagnetic radiation energy to human health.
The electromagnetic shielding materials adopted at present are mainly metals and composite materials thereof, and are manufactured into metal shells, metal nets, foamed metals, metal coatings and the like, and the metal shells, the metal nets, the foamed metals, the metal coatings and the like are covered or coated on equipment needing protection. However, because metal has the defects of high density, easy corrosion, difficult processing, difficult adjustment of shielding performance, poor wave absorbing performance at high frequency and the like, under certain conditions, electromagnetic disorder can be generated inside the electromagnetic shielding material, interference can be caused on internal components of equipment, the equipment is damaged, and the use of metal in electromagnetic shielding is severely limited. Therefore, a material with high flexibility, corrosion resistance, easy processing, low cost and good wave absorption is urgently needed to be applied to the field of electromagnetic shielding.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a carbon fiber cloth-nano copper composite material.
The invention also aims to provide the carbon fiber cloth-nano copper composite material prepared by the method.
The invention further aims to provide application of the carbon fiber cloth-nano copper composite material as an electromagnetic shielding material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a carbon fiber cloth-nano copper composite material comprises the following preparation steps:
and (3) pretreating the carbon fiber cloth, spraying a copper-containing solution and a reducing solution on the surface of the pretreated carbon fiber cloth, and drying to obtain the carbon fiber cloth-nano copper composite material.
Further, the copper-containing solution is an aqueous solution containing copper sulfate pentahydrate, sodium potassium tartrate and sodium hydroxide.
Furthermore, the concentration of copper sulfate pentahydrate in the copper-containing solution is 10-40 g/L, the concentration of potassium sodium tartrate is 60-100 g/L, and the concentration of sodium hydroxide is 20-40 g/L.
Further, the reducing solution is a sodium borohydride solution.
Further, the concentration of sodium borohydride in the reduction solution is 10-50 g/L.
Further, the spraying conditions are as follows: the spraying distance is 10-20 cm, and the temperature of the copper-containing solution is 30-60 ℃.
Further, the drying refers to drying for 10-20 hours in a vacuum drying oven at 30-50 ℃.
Further, the pretreatment is to sequentially carry out photoresist removing treatment, coarsening treatment, sensitizing treatment and activating treatment.
Further, the photoresist removing treatment is to burn for 2-4 hours at the temperature of 200-450 ℃ to remove the photoresist; the roughening treatment is soaking treatment in roughening solution prepared from potassium dichromate, sulfuric acid and water; the sensitization treatment refers to soaking treatment in a sensitization liquid prepared from stannous chloride, hydrochloric acid and water; the activation treatment is soaking treatment in an activation solution prepared from palladium chloride, hydrochloric acid and water.
Further, the concentration of potassium dichromate in the roughening solution is 15-30 g/L, sulfuric acid refers to 98 wt.% sulfuric acid, and the concentration of 98 wt.% sulfuric acid is 80-150 ml/L; the concentration of stannous chloride in the sensitizing solution is 3-20 g/L, hydrochloric acid refers to 37 wt.% hydrochloric acid, and the concentration of the 37 wt.% hydrochloric acid is 20-80 ml/L; the concentration of palladium chloride in the activation solution is 0.05-0.2 g/L, hydrochloric acid refers to 37 wt.% hydrochloric acid, and the concentration of 37 wt.% hydrochloric acid is 0.8-2 ml/L.
Further, soaking in the roughening solution for 5-30 min at 20-50 ℃, and cleaning with deionized water after soaking; soaking in the sensitizing solution for 10-20 min, and cleaning with deionized water after soaking; and the time of soaking treatment in the activating solution is 10-20 min, and the activating solution is washed by deionized water after soaking treatment.
A carbon fiber cloth-nano copper composite material is prepared by the method.
The carbon fiber cloth-nano copper composite material is applied as an electromagnetic shielding material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method for spraying the nano-copper on the surface of the carbon fiber cloth has simple process, is easy to realize, has low cost compared with the traditional carbon fiber chemical copper plating or magnetron sputtering process, and is suitable for batch production.
(2) The obtained carbon fiber cloth-nano copper composite material has excellent wave-absorbing performance, uniform copper coating, good conductivity and good bending resistance. Meanwhile, the defects of poor flexibility, heavy weight, high production cost, easy corrosion and the like of the traditional metal material are overcome. Can be used as electromagnetic shielding material with excellent performance.
(3) The carbon fiber cloth-nano copper composite material obtained by the invention has the characteristics of light weight, ultra-thin property and good flexibility.
Drawings
Fig. 1 and 2 are XRD composition analysis charts of the original woven carbon fiber cloth and the obtained carbon fiber cloth-nano copper composite material in example 1, respectively.
Fig. 3 and 4 are SEM topography analysis diagrams of the original carbon fiber woven cloth and the obtained carbon fiber cloth-nano copper composite material in example 1, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The carbon fiber cloth-nano copper composite material of the embodiment is prepared by the following method:
(1) degumming treatment of carbon fiber woven cloth
Putting the carbon fiber woven cloth into a muffle furnace for degumming treatment, heating at 200 ℃ for 2h, taking out, putting into absolute ethyl alcohol, ultrasonically cleaning for 5min, taking out, cleaning with deionized water, and blow-drying.
(2) Coarsening treatment of carbon fiber woven cloth
Soaking the carbon fiber woven cloth obtained in the step (1) in a roughening solution for 15min at the temperature of 40 ℃; taking out, washing with deionized water, and blow-drying for later use; the coarsening liquid is an aqueous solution with the concentration of potassium dichromate of 20g/L and the concentration of 98 wt.% sulfuric acid of 100 ml/L.
(3) Sensitization treatment of carbon fiber woven cloth
And (3) placing the carbon fiber woven cloth subjected to the roughening treatment in the step (2) into a stannous chloride aqueous solution with the concentration of 10g/L and 37 wt.% hydrochloric acid with the concentration of 50ml/L, soaking for 15min, taking out, washing with deionized water, and drying for later use.
(4) Activation treatment of carbon fiber woven cloth
And (4) putting the carbon fiber woven cloth subjected to sensitization treatment in the step (3) into an activation solution with the concentration of palladium chloride being 0.1g/L and the concentration of 37 wt.% hydrochloric acid being 1ml/L, soaking for 15 minutes, taking out, and then washing and drying with deionized water for later use.
(5) Copper spraying treatment on surface of carbon fiber woven cloth
Fixing the carbon fiber woven cloth treated in the step (4) on a spraying device, then respectively spraying a copper-containing solution and a reducing solution for 10 times on the front side and the back side of the carbon fiber woven cloth at a distance of 10cm from the carbon fiber woven cloth by using a spraying pot every 10s, wherein the reducing solution is an aqueous solution with 20g/L of sodium borohydride, the copper-containing solution is an aqueous solution with 30g/L of copper sulfate pentahydrate, 70g/L of potassium sodium tartrate and 25g/L of sodium hydroxide, and the temperature of the copper-containing solution is 40 ℃. And spraying the front surface and the back surface of the carbon fiber cloth for 60 times, taking out, washing with deionized water, and drying in a vacuum drying oven at the drying temperature of 35 ℃ for 10 hours to obtain the carbon fiber cloth-nano copper composite material.
The prepared carbon fiber cloth-nano copper composite material is characterized as follows:
(1) and (3) component analysis: the surface of the sample is subjected to composition analysis by an X-ray diffractometer (XRD), and XRD patterns of the original carbon fiber woven cloth and the obtained carbon fiber cloth-nano copper composite material are respectively shown as figure 1 and figure 2. As can be seen in FIG. 2, the characteristic peak of copper appears together with Cu2The characteristic peak of O shows that the metal coating obtained by the two-component spraying method is a copper-clad layer, and a small amount of Cu is generated2O。
(2) And (3) morphology analysis: SEM appearance analysis graphs of the original carbon fiber woven cloth and the obtained carbon fiber cloth-nano copper composite material are respectively shown in FIG. 3 and FIG. 4. Fig. 4 shows that the copper-clad layer obtained by the spraying method is nano copper, the copper-clad layer is compact, uniform in structure and good in performance, and the carbon fiber woven fabric and the copper-clad layer are firmly adhered.
(3) And (3) testing the electromagnetic shielding performance: the effective shielding effectiveness reaches more than 55dB when the test is carried out in the frequency range of 30 MHz-1500 MHz. Can be used as electromagnetic shielding material with excellent performance.
Example 2
The carbon fiber cloth-nano copper composite material of the embodiment is prepared by the following method:
(1) degumming treatment of carbon fiber woven cloth
Putting the carbon fiber woven cloth into a muffle furnace for degumming treatment, heating at 250 ℃ for 2.5h, taking out, putting into absolute ethyl alcohol, ultrasonically cleaning for 5min, taking out, cleaning with deionized water, and blow-drying.
(2) Coarsening treatment of carbon fiber woven cloth
Soaking the carbon fiber woven cloth obtained in the step (1) in a roughening solution for 20min at the temperature of 45 ℃; taking out, washing with deionized water, and blow-drying for later use; the coarsening liquid is an aqueous solution with the concentration of potassium dichromate of 25g/L and the concentration of 98 wt.% sulfuric acid of 110 ml/L.
(3) Sensitization treatment of carbon fiber woven cloth
And (3) placing the carbon fiber woven cloth subjected to the roughening treatment in the step (2) into a stannous chloride aqueous solution with the concentration of 15g/L and 37 wt.% hydrochloric acid with the concentration of 60ml/L, soaking for 15min, taking out, washing with deionized water, and drying for later use.
(4) Activation treatment of carbon fiber woven cloth
And (4) putting the carbon fiber woven cloth subjected to sensitization treatment in the step (3) into an activation solution with the concentration of palladium chloride being 0.15g/L and the concentration of 37 wt.% hydrochloric acid being 1.5ml/L for soaking for 15 minutes, taking out, and then washing and drying with deionized water for later use.
(5) Copper spraying treatment on surface of carbon fiber woven cloth
Fixing the carbon fiber woven cloth processed in the step (4) on a spraying device, then respectively spraying a copper-containing solution and a reducing solution for 15 times on the front side and the back side of the carbon fiber woven cloth at a distance of 12cm from the carbon fiber woven cloth by using a spraying pot every 10s, wherein the reducing solution is an aqueous solution with 25g/L of sodium borohydride, the copper-containing solution is an aqueous solution with 35g/L of copper sulfate pentahydrate, 80g/L of sodium potassium tartrate and 30g/L of sodium hydroxide, and the temperature of the copper-containing solution is 45 ℃. And (3) spraying the front surface and the back surface for 80 times, taking out, washing with deionized water, and drying in a vacuum drying oven at the drying temperature of 35 ℃ for 15 hours to obtain the carbon fiber cloth-nano copper composite material.
The analysis on the components and the morphology of the carbon fiber cloth-nano copper composite material obtained in the embodiment is the same as that in the embodiment 1, the copper-clad layer is compact, the structure is uniform, the performance is good, and the carbon fiber woven cloth and the copper-clad layer are firmly adhered. The effective shielding effectiveness reaches more than 55dB when the test is carried out in the frequency range of 30 MHz-1500 MHz. The electromagnetic shielding composite material has the advantages of high flexibility, easiness in processing, low cost and good wave absorption.
Example 3
The carbon fiber cloth-nano copper composite material of the embodiment is prepared by the following method:
(1) degumming treatment of carbon fiber woven cloth
Putting the carbon fiber woven cloth into a muffle furnace for degumming treatment, heating at 270 ℃ for 3h, taking out, putting into absolute ethyl alcohol, ultrasonically cleaning for 5min, taking out, cleaning with deionized water, and blow-drying.
(2) Coarsening treatment of carbon fiber woven cloth
Soaking the carbon fiber woven cloth obtained in the step (1) in a roughening solution for 15min at the temperature of 50 ℃; taking out, washing with deionized water, and blow-drying for later use; the coarsening liquid is an aqueous solution with the concentration of potassium dichromate of 30g/L and the concentration of 98 wt.% sulfuric acid of 130 ml/L.
(3) Sensitization treatment of carbon fiber woven cloth
And (3) placing the carbon fiber woven cloth subjected to the roughening treatment in the step (2) into a stannous chloride aqueous solution with the concentration of 20g/L and 37 wt.% hydrochloric acid with the concentration of 70ml/L, soaking for 15min, taking out, washing with deionized water, and drying for later use.
(4) Activation treatment of carbon fiber woven cloth
And (4) putting the carbon fiber woven cloth subjected to sensitization treatment in the step (3) into an activation solution with the concentration of palladium chloride of 0.2g/L and the concentration of 37 wt.% hydrochloric acid of 2ml/L for soaking for 15 minutes, taking out, and then washing and drying with deionized water for later use.
(5) Copper spraying treatment on surface of carbon fiber woven cloth
Fixing the carbon fiber woven cloth processed in the step (4) on a spraying device, then respectively spraying a copper-containing solution and a reducing solution for 10 times on the front side and the back side of the carbon fiber woven cloth at a distance of 15cm from the carbon fiber woven cloth every 10s by using a spraying pot, wherein the reducing solution is an aqueous solution with 30g/L of sodium borohydride, the copper-containing solution is an aqueous solution with 40g/L of copper sulfate pentahydrate, 80g/L of potassium sodium tartrate and 40g/L of sodium hydroxide, and the temperature of the copper-containing solution is 50 ℃. And (3) spraying the front surface and the back surface of the carbon fiber cloth for 100 times, taking out, washing with deionized water, and drying in a vacuum drying oven at the drying temperature of 35 ℃ for 20 hours to obtain the carbon fiber cloth-nano copper composite material.
The analysis on the components and the morphology of the carbon fiber cloth-nano copper composite material obtained in the embodiment is the same as that in the embodiment 1, the copper-clad layer is compact, the structure is uniform, the performance is good, and the carbon fiber woven cloth and the copper-clad layer are firmly adhered. The effective shielding effectiveness reaches more than 55dB when the test is carried out in the frequency range of 30 MHz-1500 MHz. The electromagnetic shielding composite material has the advantages of high flexibility, easiness in processing, low cost and good wave absorption.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a carbon fiber cloth-nano copper composite material is characterized by comprising the following preparation steps:
pretreating the carbon fiber cloth, spraying a copper-containing solution and a reducing solution on the surface of the pretreated carbon fiber cloth at the same time, and drying to obtain a carbon fiber cloth-nano copper composite material;
the copper-containing solution is an aqueous solution containing copper sulfate pentahydrate, potassium sodium tartrate and sodium hydroxide; the concentration of copper sulfate pentahydrate in the copper-containing solution is 10-40 g/L, the concentration of potassium sodium tartrate is 60-100 g/L, and the concentration of sodium hydroxide is 20-40 g/L;
the reducing solution is a sodium borohydride solution; the concentration of sodium borohydride in the reduction solution is 10-50 g/L.
2. The method for preparing a carbon fiber cloth-nano copper composite material as claimed in claim 1, wherein the spraying conditions are as follows: the spraying distance is 10-20 cm, and the temperature of the copper-containing solution is 30-60 ℃.
3. The preparation method of the carbon fiber cloth-nano copper composite material according to claim 1, wherein the preparation method comprises the following steps: the drying is drying for 10-20 hours in a vacuum drying oven at 30-50 ℃.
4. The preparation method of the carbon fiber cloth-nano copper composite material according to claim 1, wherein the preparation method comprises the following steps: the pretreatment is to sequentially carry out photoresist removing treatment, coarsening treatment, sensitizing treatment and activating treatment.
5. The preparation method of the carbon fiber cloth-nano copper composite material according to claim 4, wherein the preparation method comprises the following steps: the photoresist removing treatment is to burn at the temperature of 200-450 ℃ for 2-4 h for photoresist removing treatment; the roughening treatment is soaking treatment in roughening solution prepared from potassium dichromate, sulfuric acid and water; the sensitization treatment refers to soaking treatment in a sensitization liquid prepared from stannous chloride, hydrochloric acid and water; the activation treatment is soaking treatment in an activation solution prepared from palladium chloride, hydrochloric acid and water.
6. The preparation method of the carbon fiber cloth-nano copper composite material according to claim 5, wherein the preparation method comprises the following steps: the concentration of potassium dichromate in the roughening solution is 15-30 g/L, sulfuric acid refers to 98 wt.% sulfuric acid, and the concentration of 98 wt.% sulfuric acid is 80-150 ml/L; the concentration of stannous chloride in the sensitizing solution is 3-20 g/L, hydrochloric acid refers to 37 wt.% hydrochloric acid, and the concentration of the 37 wt.% hydrochloric acid is 20-80 ml/L; the concentration of palladium chloride in the activation solution is 0.05-0.2 g/L, hydrochloric acid refers to 37 wt.% hydrochloric acid, and the concentration of 37 wt.% hydrochloric acid is 0.8-2 ml/L; soaking in the roughening solution for 5-30 min at 20-50 ℃, and cleaning with deionized water after soaking; soaking in the sensitizing solution for 10-20 min, and cleaning with deionized water after soaking; and the time of soaking treatment in the activating solution is 10-20 min, and the activating solution is washed by deionized water after soaking treatment.
7. A carbon fiber cloth-nano copper composite material is characterized in that: prepared by the method of any one of claims 1 to 6.
8. Use of the carbon fiber cloth-nano copper composite material as claimed in claim 7 as an electromagnetic shielding material.
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| CN112482024B (en) * | 2020-11-26 | 2022-09-23 | 南京信息工程大学 | Preparation method of copper-plated carbon fabric electromagnetic shielding material |
| CN112626842A (en) * | 2020-12-02 | 2021-04-09 | 陕西科技大学 | Copper oxide nanowire composite material grown on carbon fiber woven cloth and preparation method thereof |
| CN115161737A (en) * | 2022-05-11 | 2022-10-11 | 北京邮电大学 | Method for preparing electromagnetic shielding material for copper electrodeposition on surface of flexible substrate |
| CN115807204A (en) * | 2022-11-25 | 2023-03-17 | 国网黑龙江省电力有限公司大兴安岭供电公司 | Method for metalizing surface of carbon fiber composite material and application thereof |
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