EP0149763A2 - Verfahren und Vorrichtung zur Elektroplattierung von Kohlenstoffasern - Google Patents
Verfahren und Vorrichtung zur Elektroplattierung von Kohlenstoffasern Download PDFInfo
- Publication number
- EP0149763A2 EP0149763A2 EP84114440A EP84114440A EP0149763A2 EP 0149763 A2 EP0149763 A2 EP 0149763A2 EP 84114440 A EP84114440 A EP 84114440A EP 84114440 A EP84114440 A EP 84114440A EP 0149763 A2 EP0149763 A2 EP 0149763A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon fiber
- fiber strand
- plating bath
- electroplating method
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 126
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims description 49
- 238000009713 electroplating Methods 0.000 title claims description 40
- 238000007747 plating Methods 0.000 claims abstract description 123
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000002184 metal Substances 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000008151 electrolyte solution Substances 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000002203 pretreatment Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 42
- 239000000835 fiber Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- -1 etc. Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000032365 Electromagnetic interference Diseases 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 239000011556 non-electrolytic solution Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000011701 zinc 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
- C25D7/0614—Strips or foils
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/127—Metals
Definitions
- This invention relates to an electroplating method for carbon fiber strands and apparatus therefor.
- carbon fiber-reinforced con- posite materials which use carbon fibers as reinforcing fibers has been striking.
- metal-coated carbon fibers are used as reinforcing fibers for electrically non-conductive materials such as thermosetting resins, thermoplastic resins, rubbers, papers, etc.
- composite materials result having excellent mechanical properties and greatly improved electric conductivity.
- EMI shield materials Electro Magnetic Interference
- thermoplastic resin composite materials reinforced by metal-coated carbon fibers using thermoplastic resins such as polyamide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polycarbonate, polyacetal, polysulfone, an acrylonitrile- butadiene-styrene resin, polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, etc., as the matrix material
- thermosetting resin composite materials reinforced by metal-coated fibers using thermosetting resins such as an epoxy resin, an unsaturated polyester resin, a phenol resin, etc., as the matrix material are excellent EMI shield materials having good mechanical properties and good formability.
- carbon fiber-reinforced metal composite materials wherein the same metal as used for coating carbon fibers is used as the matrix material, are excellent as light-weight structural materials, electrically conductive materials, slide materials, etc.
- one method involves passing an electric current through a metallic roller and then bringing a carbon fiber strand into contact with the roller to pass the electric current to the carbon fiber strand, but in such a method it is impossible to bring every filanent of the carbon fiber strand into contact with the roller, and therefor the electric current is passed through carbon fibers which are not in contact with the roller by the contact with the carbon fibers which are in contact with the roller.
- the specific resistance of carbon fibers is of the order of 10 -3 ⁇ cm, which is much larger than the specific resistance of an ordinary metal of about 10 6 ⁇ cm.
- the contact resistance between the carbon fibers and a roller is large enough to generate heat, and the metal coating formed on the carbon fibers by electroplating tends to be oxidized by oxygen in the air and also by ozone generated by sparks occurring between the carbon fibers and the roller, which results in the occurrence of uneven color tone of the metal-coated carbon fiber strand, and the so-called plating defects such as burnt marks, lateral stripe marks, etc. If the metal coating is oxidized, the specific resistance of the metal-coated carbon fiber strand is increased, reducing the effect thereof as an EMI shield material.
- An object of this invention is to provide an electroplating method for carbon fiber strands capable of overcoming the above-described difficulties and causing no uneven color tone and plating defects, and also to provide an apparatus for performing the method.
- a further object of this invention is to provide a method for continuously applying electroplating uniformly onto every filament of a carbon fiber strand and to provide an apparatus for performing the method.
- a continuous electroplating method for a carbon fiber strand which comprises continuously introducing a carbon fiber strand into an inlet of a metal plating bath and removing the carbon fiber from an outlet of the metal plating bath and applying an electric current to the'carbon fiber strand in a liquid or an inert gas atmosphere outside of the metal plating bath and performing electroplating in the metal plating bath with the carbon fiber strand as the cathode.
- a continuous electroplating apparatus for a carbon fiber strand for performing electroplating with the carbon fiber strand as a cathode, comprising an electroplating bath having an electric current applying section to the carbon fiber strand disposed in a liquid or an inert gas atmosphere outside the plating bath.
- carbon fiber strand in this specification is meant a carbon fiber strand or a graphite fiber strand usually composed of from about 100 to 100,000, and more generally from about 1,000 to 50,000, continuous fibers.
- the application of an electric current to the carbon fiber strand is generally performed by passing an electric current through a conductive roller such as a metallic roller and contacting the carbon fiber strand with the surface of the roller.
- a conductive roller such as a metallic roller and contacting the carbon fiber strand with the surface of the roller.
- the whole conductive roller or at least the contacting portion of the conductive roller with a carbon fiber strand is disposed in a liquid or an inert gas atmosphere.
- the application of an electric current to the carbon fiber strand is performed at the position of the carbon fiber strand outside of the plating bath and in this case, the section of the application of electric current to a carbon fiber strand may be the inlet side or the outlet side of the plating bath, or may be both sides of the plating bath, but it is particularly preferred that an electric current is applied to a carbon fiber strand at the outlet side of the plating bath.
- the liquid for use in this invention may be a non- electrolytic solution but is preferably an electrolytic solution.
- the liquid for use in this invention if the liquid is inactive with respect to the fibers to be plated, however, when two or more plating baths are used and the section of applying electric current to the carbon fiber strand is disposed before at least one plating bath, it is preferred to use, for example, an aqueous solution containing the same component or components as that or those of the plating bath, and more preferably an electrolytic solution having the same composition as that of the plating bath, or an aqueous solution containing only the main component of the plating bath at a concentration from at least 20% of the concentration thereof in the plating bath to less than the concentration of the main component in the saturated solution thereof at the plating temperature.
- the concentration of the composition in the aqueous solution is slightly lower, preferably more than 5% lower, more preferably more than 10% lower than that of the plating bath, since the concentration of a plating bath tends to increase during plating.
- the main component of a plating bath is meant a salt of the metal which is plated on fibers.
- the aqueous solution as described above can be used as the liquid, but the aqueous solution need not always necessarily be the same as the aqueous solution, and water and any other aqueous solution of an electrolyte .
- an inorganic salt for example, NaCl, Na 2 CO 3 , KCl, NH 4C l, CuS0 4 , NiS0 4 ZnCl 2 , etc., can also be used.
- the concentration of the solution is controlled so that the specific electric conductivity is preferably within the range of from 1x10 -2 to 1 ⁇ -1 ⁇ cm -1 , more preferably from 2x10 -2 to 5x10 -1 ⁇ -1 ⁇ cm -1 .
- the inert gas for use in this invention is, for example, N Z , Ar,, He, etc.
- the conductive roller for the application of electric current be disposed at the outlet side of the carbon fiber strand.
- the generation of heat by the contact resistance between the conductive roller and a carbon fiber strand can be minimized since the contact portion of the roller with the carbon fiber strand is in the liquid, whereby the oxidation of the coated metal formed on the fibers by electroplating does not occur.
- the contact portion of the roller with the carbon fibers is in an oxygen-free state since the portion is in the inert gas atmosphere, whereby the oxidation of the coated metal by high temperature oxidation, ozone oxidation, etc., does not occur even when heat is generated by the contact resistance. Accordingly, a metal-coated carbon fiber strand having neither uneven color tone nor so-called plating defects such as burnt marks, stripe marks, etc., can be obtained in this invention.
- the electric plating method of this invention can be used for plating a metal such as Cu, Ni, Cr, Zn, Cd, Pb, Sn, Au, Ag, etc., or alloys of at least two these metals, which can be used for ordinary electric plating.
- the plating bath compositions for use in this invention are conventional, and examples of the plating bath compositions are as follows.
- Fig. 1, Fig. 2 and Fig. 3 are schematic views each showing an example of the apparatus for performing the method of this invention.
- a carbon fiber strand 5 enters a plating bath 11 containing a plating bath composition 4 through inlet side nip rollers 6 and then is introduced to outlet side nip rollers 7 through an inlet side guide roller 8 and an outlet side guide roller 9, and through a seal box 2 in the case of Fig. 1 or a liquid bath 3 containing a liquid 12 in the case of Fig. 2.
- the inside of the seal box 2 is filled with an inert gas such as N 21 Ar, He, etc., the pressure of which is slightly higher than the atmospheric pressure so that oxygen in air does not enter. Since the seal box 2 is connected to the plating bath 11, the seal box is shielded from external atmosphere. An electric current is applied to the carbon fiber strand 5 by contact with the surface of a conductive roller 1 for applying electric current placed in the seal box 2 or a liquid bath 3 ( Figure 2), whereby a metal is plated on each filament of the carbon fiber strand 5 in the plating composition 4.
- an inert gas such as N 21 Ar, He, etc.
- the electric current applying roller 1 is disposed in a seal box 2 as shown in Fig. 1 or in a liquid bath 3 as shown in Fig. 2 so that, in the latter case, the contact portion of the roller 1 with the carbon fiber strand 5 is in a liquid 12 in the bath 3.
- Numeral 10 shows a metal anode.
- Numerals 13 and 14 show guide rollers.
- Fig. 3 shows the use of two or more plating baths and gas seal boxes which can be used in the manner of the apparatus shown in Fig. 1.
- Fig. 4 shows the use of two or more plating baths and liquid baths :which can be used in the manner of the apparatus shown in Fig. 2.
- each filament of a fiber strand Upon applying plating to each filament of a fiber strand, it is required to form proper space among the filaments for impregnating a liquid plating composition in the spaces among the filaments and also it is required to reduce the current density, and prolong the treatment period, and to adjust deposition of a metal onto the fiber in order to prevent bridging of the plated coating formed on the surface of the fiber strands, which disturbs the impregnation of the plating liquid composition into the inside of the fiber strand.
- An aqueous electrolytic solution containing the main component of the plating bath composition is applied to a carbon fiber strand so that the inside of the carbon fiber strand is impregnated with the solution.
- the application of the electrolytic solution onto a carbon fiber strand is performed by passing the carbon fiber strand through a bath containing the electrolytic solution or by spraying the electrolytic solution onto the carbon fiber strand by a shower, etc.
- the content of the electrolytic solution impregnated in the carbon fiber strand is usually up to 200% by weight, and preferably higher than 5% by weight, based on the weight of the carbon fiber strand.
- the elctrolytic solution usually contains, for example, a nickel salt, a Na, Ni or ammonium chloride, and a pH buffer in the case of nickel plating.
- the electrolytic solution which is applied in a preliminary step to the carbon fiber strand may contain a nickel salt alone, which is the main component in the case of nickel plating, or may contain a nickel salt, a chloride as described above, and a pH buffer.
- the concentration of the electrolytic solution for use in the case of preliminary application to a carbon fiber strand is from 20% of the concentration of the plating bath composition to less than the concentration of the saturated aqueous solution of the main component in the plating bath composition, more preferably from 50% of the concentration of the component to 90% of the concentration of the saturated aqueous solution of the component. If the concentration of the electrolytic solution is less than 20%, the difference of metal ion concentration between the surroundings of the carbon fiber strand and the central portion thereof in the plating bath is liable to become large and the thickness of the metal coating becomes uneven to cause the formation of lateral stripes.
- the temperature at the application of the electrolytic solution onto the carbon fiber strand is generally in the range of from 10 to 80°C, and preferably from 20 to 50°C.
- a conventional fiber opening method for fiber strands i.e., a mechanical method, an electrical method, a method of utilizing a gas such as air, etc., can be used.
- the methods described in Japanese Patent Application No. JP-A- 131,023/'79, Japanese Patent Application No. JP-A- 106571/'84, etc., and a method using a guide roller or a guide bar can be utilized.
- the roller or bar composed of a metal, glass, ceramic, etc., and having a radius or a curvature radius of 10 to 100 mm is preferably used. If the radius or curvature radius is less than 10 mm, the carbon fiber strand is damaged and filaments are cut to form fuzz, and if the radius or curvature radius is over 100 mm, the spreading of the carbon fiber strand becomes insufficient. By spreading the carbon fiber strand, every filament constituting the carbon fiber strand is uniformly plated without forming lateral stripes.
- Fig. 5 and Fig. 6 are schematic'views showing examples of the apparatus for performing the above-described pretreatments in the method of this invention.
- a carbon fiber strand 5 is impregnated with an electrolytic solution by being passed through a pre-treatment bath 16 containing the electrolytic solution 15 containing the main component of a plating bath 11 and after the application of electric current by means of an electric current applying roller 18, is introduced into a plating bath 11.
- a metal anode 10 a plating liquid composition 4 and a guide roller 8 are positioned, and the carbon fiber strand 5 is continuously passed through plating liquid composition 4.
- a fiber spreading section having, for example, a guide rollers (or guide bars) 17 before the pre-treatment bath 16 containing an electrolytic solution 15 containing the main component of the plating bath 11.
- a carbon fiber strand composed of 12,000 filaments each having 7 p diameter was continuously subjected to nickel plating using the apparatus shown in Fig. 1 having a seal box filled with an argon gas at a pressure of 1.2 atom (1.2x10 5 Pa) at a temperature of 30°C.
- the plating bath composition was a hard nickel ordinary bath composition containing 150 g/liter of nickel sulfate, 15 g/liter of ammonium chloride and 15 g/liter of boric acid and the pH and the temperature of the plating bath composition were 6.0 and 25°C, respectively.
- the travelling speed of the carbon fiber strand was 30 cm/min., the residence time in the plating bath was 5 minutes and the total electric current was 10 amperes.
- nickel plating was applied to carbon fiber strands under the same conditions as above except that the seal box was filled with air in place of argon gas.
- Nickel plating was applied to carbon fiber strands using the apparatus shown in Fig. 2 having a liquid bath for applying electric current containing an electrolytic.solution having the same composition as that of the plating bath composition under the same conditions as in Example 1.
- the thickness of the nickel coating and the specific resistance of the nickel-coated carbon fiber strand were measured and the results thus obtained are shown in Table 1.
- a resin composite material or a metal composite material using the product obtained in the foregoing examples of the present invention as the reinforcing material was excellent as an EMI shield material, a light-weight structural material, a conductive material, etc.
- a carbon fiber Besfight, HTA 7-12000 (Trade name of carbon fiber strand of 12,000 filaments having a diameter of 7 p made by Toho Beslon Co., Ltd.) was continuously subjected to nickel plating.
- the travelling speed of the carbon fiber strand was 20 cm/min.
- the residence time in the plating bath was 5 min.
- the total electric current was 10 amperes
- the bath temperature was 25°C.
- the plating bath composition was a hard nickel ordinary plating composition containing 150 g/liter of nickel sulfate, 15 g/ liter of ammonium chloride, and 15 g/liter of boric acid.
- a pre-treatment bath for preliminary application of an electrolytic solution to the carbon fiber strand was filled with an aqueous solution of 150 g/liter of nickel sulfate (100% of the nickel sulfate concentration of the plating bath composition) and the temperature of the pre-treatment bath was 25°C.
- the carbon fiber strand was passed through the pre-treatment bath, whereby the strand was impregnated with the electrolytic solution at a content of about 50%.
- three fiber opening guide rollers each having a radius of 25 mm were disposed in a straight line before the pre-treatment bath with a distance between the centers of the axes of 75 mm.
- the cross-sections of the nickel-plated carbon fiber strands were observed by a scanning type electron microscope and the mean thickness of the nickel coating of the whole fiber strand, the thickness thereof on the fibers in the outermost portion of the strand, and the thickness thereof on the fibers in the central portion of the strand were measured.
- the outer portion is the portion of a fiber strand outside the portion of the 1/2 of the distance of the strand from the center of the strand-in the radial direction of the strand, and the central portion is the remaining portion thereof.
- nickel plating was applied to the carbon fiber strand under the same conditions as above without preliminary applying the electrolytic solution to the carbon fiber strand and the thickness of nickel coating was measured in the same way as above. The results thus obtained are shown in Table 2.
- the pre-treatment bath as in Example 3 was filled with an aqueous solution of 20 g/liter, 90 g/liter, or 150 g/ liter of nickel sulfate or a nickel sulfate saturated aqueous solution of 30°C, and nickel plating was applied under the same conditions as in Example 3. The results thus obtained are shown in Table 3.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Electroplating Methods And Accessories (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22337583A JPS60119267A (ja) | 1983-11-29 | 1983-11-29 | 炭素繊維束の電気メッキ方法 |
JP223375/83 | 1983-11-29 | ||
JP8340284A JPS60231864A (ja) | 1984-04-24 | 1984-04-24 | 炭素繊維束の電気メツキ方法 |
JP83402/84 | 1984-04-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0149763A2 true EP0149763A2 (de) | 1985-07-31 |
EP0149763A3 EP0149763A3 (de) | 1985-08-21 |
Family
ID=26424429
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84114440A Withdrawn EP0149763A3 (de) | 1983-11-29 | 1984-11-29 | Verfahren und Vorrichtung zur Elektroplattierung von Kohlenstoffasern |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP0149763A3 (de) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0251491A1 (de) * | 1986-05-30 | 1988-01-07 | Amoco Corporation | Mehrfache elektrolytische Behandlung von Kohlenstoffasern zur Verbesserung des Abscherwiderstandes |
EP0415876A1 (de) * | 1989-08-07 | 1991-03-06 | Eltech Systems Corporation | Kontinuierliche Elektroplattierung von elektrisch leitendem Schaum |
FR2876044A1 (fr) * | 2004-10-05 | 2006-04-07 | Ensmse | Procede d'electrodeposition de nanoparticules de metal sur un filtre en materiau fibreux, materiau ainsi obtenu et son utilisation pour l'elimination de polluants en milieu gazeux |
WO2013083696A2 (de) | 2011-12-07 | 2013-06-13 | Toho Tenax Europe Gmbh | Kohlenstofffaser für verbundwerkstoffe mit verbesserter leitfähigkeit |
US9065139B2 (en) | 2009-02-04 | 2015-06-23 | National Institute Of Advanced Industrial Science And Technology | Fiber electrode for lithium secondary battery, fabrication method therefor, and lithium secondary battery including fiber electrode |
US9281539B2 (en) | 2009-07-14 | 2016-03-08 | Kawasakai Jukogyo Kabushiki Kaisha | Electrical storage device including fiber electrode, and method of fabricating the same |
CN110373894A (zh) * | 2018-04-13 | 2019-10-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | 高性能碳纳米管/金属复合导电纤维及其制备方法 |
US10576335B2 (en) | 2017-07-20 | 2020-03-03 | Taylor Made Golf Company, Inc. | Golf club including composite material with color coated fibers and methods of making the same |
CN115132501A (zh) * | 2022-07-08 | 2022-09-30 | 郑州仿弦新材料科技有限公司 | 超薄碳纤维电极及其制备方法、应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0088884A1 (de) * | 1982-03-16 | 1983-09-21 | Electro Metalloid Corporation | Metallisierte Fasern enthaltende Garne und Seile, Verfahren zu deren Herstellung und deren Verwendung |
-
1984
- 1984-11-29 EP EP84114440A patent/EP0149763A3/de not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0088884A1 (de) * | 1982-03-16 | 1983-09-21 | Electro Metalloid Corporation | Metallisierte Fasern enthaltende Garne und Seile, Verfahren zu deren Herstellung und deren Verwendung |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0251491A1 (de) * | 1986-05-30 | 1988-01-07 | Amoco Corporation | Mehrfache elektrolytische Behandlung von Kohlenstoffasern zur Verbesserung des Abscherwiderstandes |
EP0415876A1 (de) * | 1989-08-07 | 1991-03-06 | Eltech Systems Corporation | Kontinuierliche Elektroplattierung von elektrisch leitendem Schaum |
FR2876044A1 (fr) * | 2004-10-05 | 2006-04-07 | Ensmse | Procede d'electrodeposition de nanoparticules de metal sur un filtre en materiau fibreux, materiau ainsi obtenu et son utilisation pour l'elimination de polluants en milieu gazeux |
US9065139B2 (en) | 2009-02-04 | 2015-06-23 | National Institute Of Advanced Industrial Science And Technology | Fiber electrode for lithium secondary battery, fabrication method therefor, and lithium secondary battery including fiber electrode |
US9281539B2 (en) | 2009-07-14 | 2016-03-08 | Kawasakai Jukogyo Kabushiki Kaisha | Electrical storage device including fiber electrode, and method of fabricating the same |
WO2013083696A2 (de) | 2011-12-07 | 2013-06-13 | Toho Tenax Europe Gmbh | Kohlenstofffaser für verbundwerkstoffe mit verbesserter leitfähigkeit |
WO2013083696A3 (de) * | 2011-12-07 | 2013-10-10 | Toho Tenax Europe Gmbh | Kohlenstofffaser für verbundwerkstoffe mit verbesserter leitfähigkeit |
RU2615427C1 (ru) * | 2011-12-07 | 2017-04-04 | Тохо Тенакс Ойропе Гмбх | Углеродное волокно для композитных материалов с улучшенной электропроводностью |
US10576335B2 (en) | 2017-07-20 | 2020-03-03 | Taylor Made Golf Company, Inc. | Golf club including composite material with color coated fibers and methods of making the same |
US11213726B2 (en) | 2017-07-20 | 2022-01-04 | Taylor Made Golf Company, Inc. | Golf club including composite material with color coated fibers and methods of making the same |
US11752403B2 (en) | 2017-07-20 | 2023-09-12 | Taylor Made Golf Company, Inc. | Golf club including composite material with color coated fibers and methods of making the same |
CN110373894A (zh) * | 2018-04-13 | 2019-10-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | 高性能碳纳米管/金属复合导电纤维及其制备方法 |
CN115132501A (zh) * | 2022-07-08 | 2022-09-30 | 郑州仿弦新材料科技有限公司 | 超薄碳纤维电极及其制备方法、应用 |
Also Published As
Publication number | Publication date |
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EP0149763A3 (de) | 1985-08-21 |
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