CN114427108A - Method and system for continuously electroplating metal on surface of carbon fiber - Google Patents
Method and system for continuously electroplating metal on surface of carbon fiber Download PDFInfo
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- CN114427108A CN114427108A CN202111189919.6A CN202111189919A CN114427108A CN 114427108 A CN114427108 A CN 114427108A CN 202111189919 A CN202111189919 A CN 202111189919A CN 114427108 A CN114427108 A CN 114427108A
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- carbon fiber
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 218
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 218
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 238000009713 electroplating Methods 0.000 title claims abstract description 79
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002905 metal composite material Substances 0.000 claims abstract description 27
- 230000007480 spreading Effects 0.000 claims abstract description 23
- 238000003892 spreading Methods 0.000 claims abstract description 23
- 230000007246 mechanism Effects 0.000 claims abstract description 18
- 239000003292 glue Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 238000007654 immersion Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 239000002923 metal particle Substances 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- -1 preferably Chemical class 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000006174 pH buffer Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- RZHBMYQXKIDANM-UHFFFAOYSA-N dioctyl butanedioate;sodium Chemical compound [Na].CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC RZHBMYQXKIDANM-UHFFFAOYSA-N 0.000 claims 1
- 239000006179 pH buffering agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000004804 winding Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a method and a system for continuously electroplating metal on the surface of carbon fiber. The method comprises the following steps: continuously passing the carbon fiber through a high-temperature degumming device provided with an airflow filament spreading mechanism to carry out degumming treatment to obtain pretreated carbon fiber; and electroplating the pretreated carbon fiber to obtain the metal composite carbon fiber. The method provided by the invention has the advantages that the surface degumming effect of the carbon fiber is good, the electroplating dispersion is good, the carbon fiber can realize continuous and uniform metal electroplating under the condition of keeping the original mechanical strength, and the carbon fiber after electroplating has no black core phenomenon.
Description
Technical Field
The invention belongs to the technical field of carbon fiber metallization, and particularly relates to a method and a system for continuously electroplating metal on the surface of carbon fiber.
Background
The nickel-plated carbon fiber is a high-conductivity light fiber material which is prepared by uniformly coating a metal coating on the surface of a carbon fiber wire on the basis of continuous nano modification of the surface of the carbon fiber, has the advantages of stronger corrosion resistance, light weight, higher strength, unique conductivity and magnetic conductivity and the like compared with the traditional electromagnetic shielding material, and has important application in the fields of aerospace, military instruments, rail transit, communication electronics, new energy automobiles and the like.
The surface of the carbon fiber precursor can be coated with organic glue before leaving the factory, so that the carbon fiber is smooth in surface and easy to wind. However, the presence of the colloidal layer is not conducive to metal coating, and in particular to electroplating, on the surface of the carbon fiber. Before the carbon fiber is electroplated, the carbon fiber must be subjected to degumming treatment, and two common degumming methods are adopted, namely organic solvent degumming (utilizing the principle of similarity and intermiscibility) and high-temperature treatment (pyrolyzing a colloidal layer). The carbon fiber glue removing efficiency of the traditional glue removing method is particularly low, and particularly aims at large-tow carbon fibers, so that the deposition of metal nickel on the surface of the carbon fibers during electroplating is influenced. In addition, electric field lines are shielded by the carbon wire aggregation of the large-tow carbon fibers, so that the outer layer of one bundle of carbon fibers is deposited more during electroplating, and the inner plating layer of the bundle is not deposited, so that the phenomena of uneven electroplating and black core are caused. The prior art mainly has the following defects: (1) the chemical plating process is complex, and the thickness of a plating layer is difficult to control; (2) in the traditional method, the process of metallization of the surface of the carbon fiber is multiple and scattered, and the carbon fiber product is difficult to be continuously processed and electroplated; (3) for large-tow carbon fibers, because of a plurality of monofilaments, surface fibers have a certain shielding effect on internal fibers, and the phenomenon of uneven electroplating and black core is easy to occur in the traditional electroplating process; (4) the traditional carbon fiber electroplating process can seriously weaken the original mechanical strength of the carbon fiber. Therefore, it is an urgent problem to provide a method for continuously electroplating metal on the surface of carbon fiber.
Disclosure of Invention
The invention mainly aims to provide a method and a system for continuously electroplating metal on the surface of carbon fiber, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for continuously electroplating metal on the surface of carbon fiber, which comprises the following steps:
continuously passing the carbon fibers through a high-temperature degumming device provided with an airflow filament spreading mechanism to carry out degumming treatment to obtain pretreated carbon fibers;
and electroplating the pretreated carbon fiber to obtain the metal composite carbon fiber.
In some more specific embodiments, the air spreading mechanism at least loosens and spreads the carbon fiber monofilaments in the carbon fibers in the radial direction of the carbon fibers under the action of the air flow.
The embodiment of the invention also provides the metal composite carbon fiber prepared by the method, wherein the content of metal in the metal composite carbon fiber is 25-60 wt%.
The embodiment of the invention also provides a system for continuously electroplating metal on the surface of carbon fiber, which comprises:
the discharging device is at least used for providing carbon fibers;
the high-temperature glue removing device is provided with an airflow filament spreading mechanism and is at least used for removing organic glue on the surface of carbon fibers and enabling carbon fiber monofilaments in the carbon fibers to be loosened and spread along the radial direction of the carbon fibers under the action of airflow so as to obtain pretreated carbon fibers;
and the electroplating device is at least used for electroplating the pretreated carbon fiber to obtain the metal composite carbon fiber.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method for continuously electroplating metal on the surface of the carbon fiber has good glue removing effect and good electroplating dispersion on the surface of the carbon fiber, so that continuous and uniform metal electroplating is realized on the carbon fiber under the condition of keeping the original mechanical strength, and the electroplated product has no black core phenomenon;
(2) the carbon fiber electroplating process provided by the invention is simple and easy to integrate, and the thickness of the coating of the produced metal composite carbon fiber product is uniform and controllable;
(3) the glue removing device in the system for continuously electroplating metal on the surface of the carbon fiber is provided with the airflow filament spreading mechanism, the glue removing effect is good, the broken filaments are few, and the subsequent electroplating is more uniform due to the spreading of the filament bundles.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some embodiments recorded in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a system for continuously electroplating metal onto the surface of carbon fibers in an exemplary embodiment of the invention;
FIGS. 2a to 2c are SEM images and EDS spectra of Dongli carbon fiber in example 1 of the present invention;
FIGS. 3a to 3c are SEM images and EDS spectra of the pretreated carbon fiber in example 1 of the present invention;
FIGS. 4a to 4c are SEM images, namely EDS spectra, of the metallic nickel composite carbon fiber in example 1 of the present invention;
fig. 5 is a picture of the metallic nickel composite carbon fiber prepared in comparative example 1 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making an invasive task, are within the scope of the present invention.
Specifically, as an aspect of the technical solution of the present invention, a method for continuously electroplating metal on a surface of a carbon fiber, the method includes:
continuously passing the carbon fibers through a high-temperature degumming device provided with an airflow filament spreading mechanism to carry out degumming treatment to obtain pretreated carbon fibers;
and electroplating the pretreated carbon fiber to obtain the metal composite carbon fiber.
In some preferred embodiments, the air spreading mechanism at least loosens and spreads the carbon fiber monofilaments in the carbon fibers in the radial direction of the carbon fibers under the action of air flow, so that the carbon fibers realize a spreading effect.
The high-temperature degumming device provided by the invention is matched with an airflow filament spreading function, so that the problem of 'black core' of large tows can be solved.
In some preferred embodiments, the temperature of the degumming treatment is 400-600 ℃ and the time is 2-10 min.
In some preferred embodiments, the method further comprises: and carrying out rinsing treatment after the degumming treatment is finished.
In some preferred embodiments, the carbon fibers comprise carbon fiber tows having a filament count of 1K to 48K.
Further, the carbon fiber comprises a carbon fiber tow having a filament number of 1K, 3K, 6K, 12K, 24K, or 48K.
Furthermore, the diameter of each monofilament in the carbon fiber is 6-8 mu m.
In some preferred embodiments, the method comprises: continuously passing the pretreated carbon fibers through an electroplating solution with the pH value of 5.0-5.5 to carry out electroplating treatment, wherein the electroplating treatment process conditions comprise: the current density is 0.4-2.0A/dm2The voltage is 1.5-5.0V, and the time of electroplating treatment is 2-15 min; the electroplating solution includes a metal salt, a pH buffer, and a surfactant.
Furthermore, the concentration of the metal salt in the electroplating solution is 50-100 g/L.
Further, the metal salt includes a nickel salt and/or a copper salt; particularly preferably, the nickel salt comprises nickel sulfate and/or nickel chloride; particularly preferably, the copper salt comprises copper sulfate and/or copper phosphate.
Further, the pH buffer includes any one or a combination of two or more of boric acid, sodium citrate, and sodium acetate, and is not limited thereto.
Further, the surfactant includes any one or a combination of two or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfate, sodium dioctyl sulfosuccinate, sodium stearate, and is not limited thereto.
In some preferred embodiments, the method further comprises: and after the electroplating treatment is finished, washing and drying the obtained metal composite carbon fiber.
Further, the washing specifically includes: and carrying out normal-temperature clear water immersion cleaning, ultrasonic hot water immersion cleaning and clear water leaching treatment on the metal composite carbon fiber.
Further, the drying treatment temperature is 80-150 ℃, and the drying treatment time is 2-10 min.
In some preferred embodiments, the method further comprises: and rolling the metal composite carbon fiber obtained by drying treatment at a rolling speed of 0.5-2 m/min.
In some preferred embodiments, the metal composite carbon fiber comprises a metal nickel composite carbon fiber.
In some more specific embodiments, the method for continuously electroplating metal on the surface of the carbon fiber comprises the following steps:
(1) the carbon fiber winding drum is placed on a discharging device for conveying, the discharging device has the function of passively conveying carbon fibers with adjustable tension, and the carbon fibers are 1K, 3K, 6K, 12K, 24K and 48K carbon fiber tows with monofilament diameters of 6-8 mu m;
(2) the surface pretreatment of the carbon fiber comprises the steps of removing glue on the surface of the carbon fiber and rinsing with clear water, the carbon fiber surface glue removing device is a high-temperature tube furnace, a furnace body is communicated with the atmosphere, two ends of the furnace body are respectively an inlet and an outlet of the carbon fiber, the lower end of the furnace body is provided with an airflow yarn spreading system, and the glue removing temperature is 400-600 ℃;
(3) putting the pretreated carbon fiber into an electroplating bath for electroplating treatment, wherein the electroplating nickel solution consists of nickel sulfate, nickel chloride, boric acid and sodium dodecyl sulfate, the pH value is 5.0-5.5, and the current density is 0.4-2A/dm2The voltage is 1.5-5V;
(4) washing and drying the electroplated carbon fiber, wherein the washing process comprises normal-temperature clean water immersion washing, ultrasonic hot water immersion washing and clean water leaching in sequence, the drying device is a common high-temperature tube furnace, and the two ends of the furnace body are respectively an inlet and an outlet of the carbon fiber;
(5) and feeding the carbon fiber after electroplating and drying into a winding device, and winding into a nickel-plated carbon fiber product, wherein the winding speed is 0.5-2m/min, and the thickness of a plating layer can be controlled according to the winding speed.
In another aspect of the embodiment of the present invention, there is also provided a metal composite carbon fiber prepared by the foregoing method, wherein the metal content in the metal composite carbon fiber is 25 to 60 wt%.
Further, the metal includes and/or copper, and is not limited thereto.
Furthermore, the metal composite carbon fiber comprises carbon fiber and a metal layer distributed on the surface of the carbon fiber, wherein the metal layer is formed by tightly packing metal particles.
Further, the metal particles are formed by stacking metal atoms, and the particle size of the metal particles is nano-scale.
Further, the thickness of the metal layer is 0.2-2 μm.
Another aspect of the embodiments of the present invention also provides a system for continuously electroplating metal on a surface of a carbon fiber, including:
the discharging device is used for providing carbon fibers;
the high-temperature glue removing device is provided with an airflow filament spreading mechanism and is at least used for removing organic glue on the surface of carbon fibers and enabling carbon fiber monofilaments in the carbon fibers to be loosened and spread along the radial direction of the carbon fibers under the action of airflow so as to obtain pretreated carbon fibers;
and the electroplating device is at least used for electroplating the pretreated carbon fiber to obtain the metal composite carbon fiber.
In some preferred embodiments, the system further comprises a washing device at least for washing the carbon fiber after the plating treatment.
In some preferred embodiments, the system further comprises a drying device for at least drying the metal-plated carbon fiber after the washing treatment, thereby obtaining a metal composite carbon fiber.
In some preferred embodiments, the system further comprises a winding device for collecting the metal composite carbon fiber.
Specifically, a schematic diagram of a system for continuously electroplating metal on the surface of carbon fiber according to the present invention is shown in fig. 1, and the system comprises: blowing device, the device that removes glues, plating bath, washing tank, drying device to and coiling mechanism.
The glue removing device is provided with the airflow filament spreading mechanism, so that the effect of spreading filaments for large tows above 24K is very good, the broken filaments are few, the glue is completely removed, and the electroplating is more uniform; the surface of 1K, 3K, 6K, 12K, 24K and 48K carbon fiber tows with the monofilament diameter of 6-7 mu m is continuously and uniformly plated with nickel, the thickness of a plating layer is adjustable, and the plated product has no black core.
The technical solutions of the present invention will be further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were commercially available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Placing a carbon fiber winding drum on a discharging device for conveying, wherein the discharging device has the function of passively conveying carbon fibers with adjustable tension, and the carbon fibers are 6K carbon fiber tows (Dongli carbon fibers);
(2) the method comprises the following steps of (1) pretreating the surface of carbon fibers to obtain pretreated carbon fibers, wherein the surface pretreatment comprises the steps of removing glue on the surface of the carbon fibers and rinsing with clear water, a carbon fiber surface glue removing device is a high-temperature tube furnace, a furnace body is communicated with the atmosphere, two ends of the furnace body are respectively an inlet and an outlet of the carbon fibers, the lower end of the furnace body is provided with an airflow filament spreading mechanism, the glue removing temperature is 500 ℃, and the time is 5 min;
(3) putting the pretreated carbon fiber into an electroplating bath for electroplating treatment, wherein the electroplating solution consists of nickel sulfate, nickel chloride, boric acid and sodium dodecyl sulfate, the pH value is 5.0-5.5, and the current density is 1.0A/dm2The voltage is 2.0V;
(4) washing and drying the electroplated carbon fiber, wherein the washing process comprises normal-temperature clean water immersion washing, ultrasonic hot water immersion washing and clean water leaching in sequence, the drying device is a common high-temperature tube furnace, and the two ends of the furnace body are respectively an inlet and an outlet of the carbon fiber;
(5) feeding the carbon fiber after electroplating and drying into a winding device, and winding into metal nickel composite carbon fiber;
and (3) performance characterization: SEM images of the Dongli carbon fiber in example 1 are shown in fig. 2 a-2 b, and EDS spectra are shown in fig. 2 c; SEM images of the pretreated carbon fibers in example 1 are shown in fig. 3 a-3 b, and EDS spectra are shown in fig. 3 c; SEM images of the metallic nickel composite carbon fiber in example 1 are shown in fig. 4a to 4b, and EDS spectra are shown in fig. 4 c; as can be seen from the SEM image and the EDS spectrogram, the orion carbon fiber has a smooth surface, a diameter of 7.063 μm, a major element of C on the surface, and a trace amount of O (an organic glue contains O element); after the carbon fiber is subjected to degumming, a little of ash remained by decomposing the colloid is on the surface, the diameter is reduced, and only C element exists on the surface; the carbon fiber continuous nickel-electroplating product has rough surface, contains a plurality of tightly packed particles, the diameter is increased to 9.364 mu m, the thickness of a nickel layer reaches 2 mu m, and the mass content of nickel in an energy spectrum reaches more than 85 percent (the mass content is the nickel content on the surface of the carbon fiber, so the nickel content in the energy spectrum is higher).
Example 2
(1) Placing a carbon fiber winding drum on a discharging device for conveying, wherein the discharging device has the function of passively conveying carbon fibers with adjustable tension, and the carbon fibers are 1K carbon fiber tows (Dongli carbon fibers);
(2) the method comprises the following steps of (1) pretreating the surface of carbon fibers to obtain pretreated carbon fibers, wherein the surface pretreatment comprises the steps of removing glue on the surface of the carbon fibers and rinsing with clear water, a carbon fiber surface glue removing device is a high-temperature tube furnace, a furnace body is communicated with the atmosphere, two ends of the furnace body are respectively an inlet and an outlet of the carbon fibers, the lower end of the furnace body is provided with an airflow filament spreading mechanism, the glue removing temperature is 400 ℃, and the time is 2 min;
(3) putting the pretreated carbon fiber into an electroplating bath for electroplating treatment, wherein the electroplating solution consists of nickel sulfate, nickel chloride, sodium citrate and sodium hexadecyl sulfate, the pH value is 5.0-5.5, and the current density is 0.4A/dm2The voltage is 1.5V;
(4) washing and drying the electroplated carbon fiber, wherein the washing process comprises normal-temperature clean water immersion washing, ultrasonic hot water immersion washing and clean water leaching in sequence, the drying device is a common high-temperature tube furnace, and the two ends of the furnace body are respectively an inlet and an outlet of the carbon fiber;
(5) and (4) feeding the carbon fiber after electroplating and drying into a winding device, and winding into the metal nickel composite carbon fiber.
Example 3
(1) Placing a carbon fiber winding drum on a discharging device for conveying, wherein the discharging device has the function of passively conveying carbon fibers with adjustable tension, and the carbon fibers are 48K carbon fiber tows (Dongli carbon fibers);
(2) the method comprises the following steps of (1) pretreating the surface of carbon fibers to obtain pretreated carbon fibers, wherein the surface pretreatment comprises the steps of removing glue on the surface of the carbon fibers and rinsing with clear water, a carbon fiber surface glue removing device is a high-temperature tube furnace, a furnace body is communicated with the atmosphere, two ends of the furnace body are respectively an inlet and an outlet of the carbon fibers, the lower end of the furnace body is provided with an airflow filament spreading mechanism, the glue removing temperature is 600 ℃, and the time is 10 min;
(3) putting the pretreated carbon fiber into an electroplating bath for electroplating treatment, wherein the electroplating solution consists of copper sulfate, copper phosphate, boric acid and sodium dodecyl sulfate, the pH value is 5.0-5.5, and the current density is 2A/dm2The voltage is 5V;
(4) washing and drying the electroplated carbon fiber, wherein the washing process comprises normal-temperature clean water immersion washing, ultrasonic hot water immersion washing and clean water leaching in sequence, the drying device is a common high-temperature tube furnace, and the two ends of the furnace body are respectively an inlet and an outlet of the carbon fiber;
(5) and (4) feeding the electroplated and dried carbon fiber into a winding device to be wound into the metal copper composite carbon fiber.
Example 4
(1) Placing a carbon fiber winding drum on a discharging device for conveying, wherein the discharging device has the function of passively conveying carbon fibers with adjustable tension, and the carbon fibers are 24K carbon fiber tows (Dongli carbon fibers);
(2) the method comprises the following steps of (1) pretreating the surface of carbon fibers to obtain pretreated carbon fibers, wherein the surface pretreatment comprises the steps of removing glue on the surface of the carbon fibers and rinsing with clear water, a carbon fiber surface glue removing device is a high-temperature tube furnace, a furnace body is communicated with the atmosphere, two ends of the furnace body are respectively an inlet and an outlet of the carbon fibers, the lower end of the furnace body is provided with an airflow filament spreading mechanism, the glue removing temperature is 600 ℃, and the time is 5 min;
(3) putting the pretreated carbon fiber into an electroplating bath for electroplating treatment, wherein the electroplating solution consists of nickel sulfate, nickel chloride, sodium acetate and sodium dioctyl sulfosuccinate, the pH value is 5.0-5.5, and the current density is 1.0A/dm2The voltage is 2.0V;
(4) washing and drying the electroplated carbon fiber, wherein the washing process comprises normal-temperature clean water immersion washing, ultrasonic hot water immersion washing and clean water leaching in sequence, the drying device is a common high-temperature tube furnace, and the two ends of the furnace body are respectively an inlet and an outlet of the carbon fiber;
(5) the carbon fiber after being electroplated and dried is sent into a winding device to be wound into the metal nickel composite carbon fiber
Comparative example 1
The method of the comparative example is the same as that of example 1, except that no airflow filament spreading mechanism is arranged in the degumming device, and the obtained product has the phenomena of uneven electroplating and black heart which are visible to naked eyes, as shown in fig. 5.
In addition, the inventors of the present invention have also made experiments with reference to the above examples and by using other raw materials, process operations, and process conditions described in the present specification, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. A method for continuously electroplating metal on the surface of carbon fiber is characterized by comprising the following steps:
continuously passing the carbon fiber through a high-temperature degumming device provided with an airflow filament spreading mechanism to carry out degumming treatment to obtain pretreated carbon fiber;
and electroplating the pretreated carbon fiber to obtain the metal composite carbon fiber.
2. The method of claim 1, wherein: the airflow filament spreading mechanism at least loosens and spreads carbon fiber monofilaments in the carbon fibers along the radial direction of the carbon fibers under the action of airflow.
3. The method of claim 1, wherein: the temperature of the degumming treatment is 400-600 ℃, and the time is 2-10 min;
and/or, the method further comprises: and carrying out rinsing treatment after the degumming treatment is finished.
4. The method of claim 1, wherein: the carbon fiber comprises a carbon fiber tow with the monofilament number of 1K-48K; preferably, the diameter of each monofilament in the carbon fiber is 6-8 μm.
5. The method of claim 1, comprising: continuously passing the pretreated carbon fibers through an electroplating solution with the pH value of 5.0-5.5 to carry out electroplating treatment, wherein the electroplating treatment process conditions comprise: the current density is 0.4-2.0A/dm2The voltage is 1.5-5.0V, and the time of electroplating treatment is 2-15 min; the electroplating solution comprises metal salt, pH buffer and surfactant;
preferably, the concentration of the metal salt in the electroplating solution is 50-100 g/L;
preferably, the metal salt comprises a nickel salt and/or a copper salt; particularly preferably, the nickel salt comprises nickel sulfate and/or nickel chloride; particularly preferably, the copper salt comprises copper sulfate and/or copper phosphate;
preferably, the pH buffering agent comprises any one or a combination of more than two of boric acid, sodium citrate and sodium acetate;
preferably, the surfactant comprises any one or a combination of more than two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl sulfate, sodium dioctyl succinate and sodium stearate.
6. The method of claim 1, further comprising: after the electroplating treatment is finished, washing and drying the obtained metal composite carbon fiber;
preferably, the washing specifically comprises: carrying out normal-temperature clear water immersion cleaning, ultrasonic hot water immersion cleaning and clear water leaching treatment on the metal composite carbon fiber; preferably, the drying treatment temperature is 80-150 ℃, and the time is 2-10 min;
and/or, the method further comprises: and rolling the metal composite carbon fiber obtained by drying at a rolling speed of 0.5-2 m/min.
7. The metal composite carbon fiber produced by the method according to any one of claims 1 to 6, wherein the metal content in the metal composite carbon fiber is 25 to 60 wt%;
preferably, the metal comprises nickel and/or copper;
preferably, the metal composite carbon fiber comprises carbon fiber and a metal layer distributed on the surface of the carbon fiber, wherein the metal layer is formed by tightly packing metal particles; preferably, the metal particles are formed by stacking metal atoms, and the particle size of the metal particles is nano-scale; preferably, the thickness of the metal layer is 0.2-2 μm.
8. A system for continuously electroplating metal on the surface of carbon fiber is characterized by comprising:
the discharging device is at least used for providing carbon fibers;
the high-temperature glue removing device is provided with an airflow filament spreading mechanism and is at least used for removing organic glue on the surface of carbon fibers and loosening and spreading carbon fiber monofilaments in the carbon fibers along the radial direction of the carbon fibers under the action of airflow so as to obtain pretreated carbon fibers;
and the electroplating device is at least used for electroplating the pretreated carbon fiber to obtain the metal composite carbon fiber.
9. The system for continuously electroplating metal on the surface of carbon fiber according to claim 8, further comprising
The cleaning device is at least used for washing the carbon fiber after the electroplating treatment;
and/or the system further comprises a drying device at least used for drying the carbon fiber which is electroplated with metal and is subjected to washing treatment, so as to obtain the metal composite carbon fiber.
10. The system for continuously electroplating metal on the surface of carbon fiber according to claim 8, further comprising a rolling device for collecting the metal composite carbon fiber.
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