EP1930481A1 - Nanocarbon/aluminum composite material, process for producing the same, and plating liquid for use in said process - Google Patents

Nanocarbon/aluminum composite material, process for producing the same, and plating liquid for use in said process Download PDF

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Publication number
EP1930481A1
EP1930481A1 EP06766838A EP06766838A EP1930481A1 EP 1930481 A1 EP1930481 A1 EP 1930481A1 EP 06766838 A EP06766838 A EP 06766838A EP 06766838 A EP06766838 A EP 06766838A EP 1930481 A1 EP1930481 A1 EP 1930481A1
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European Patent Office
Prior art keywords
nanocarbon
halide
aluminum
aluminum composite
plating liquid
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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.)
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EP06766838A
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German (de)
English (en)
French (fr)
Inventor
Nobuyuki Koura
Atsushi Ehira
Ryo Murakami
Koichi Ui
Takashi Yatsushiro
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Publication of EP1930481A1 publication Critical patent/EP1930481A1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current

Definitions

  • the present invention relates to a nanocarbon/aluminum composite material, particularly suitable for use in electric conductors such as power cables and lead wires, heat exchangers such as radiators, condensers and evaporators and automotive parts, a process for production of the nanocarbon/aluminum composite material and a plating liquid for use in the nanocarbon/aluminum composite production process.
  • power cable and lead wire materials such as aluminum alloys and heat exchanger materials are required to have high electrical conductivity and high thermal conductivity. From the recent viewpoint of global environmental conservation, there is a growing need for weight and size reductions of power cables, lead wires, heat exchangers and automotive parts. It is thus desired that the materials of the power cables, lead wires, heat exchangers and automotive parts have high strength while being shaped in thinner forms.
  • CNT carbon nanotube
  • CNT carbon nanotube
  • the applicability of CNT is being examined in expectation of further performance improvements because of excellent CNT properties e.g. toughness, electrical conductivity and thermal conductivity.
  • Various metals such as copper, nickel and aluminum are used as matrices for production of CNT composite materials.
  • Patent Documents 3 and 4. it is reported that CNT/aluminum composite materials increase in strength and attain high thermal conductivity.
  • Each of the nanocarbon/aluminum composite material production processes of Patent Documents 1-4 and Non-Patent Document 1 includes a complicated series of process steps, e.g., placing an aluminum powder and CNT into an aluminum case, followed by heating at 600°C for 1.5 hour under a reduced pressure of 5.3 ⁇ 10 -1 Pa, pressurizing at 100 MPa for 60 minutes, and then, extruding at 10 MPa/min and 600°C.
  • the nanocarbon is added and mixed by stirring into the molten metal.
  • the carbon-fiber/aluminum composite material shows no sign of strength deterioration when heated at 500°C or lower in a non-oxidizing atmosphere.
  • the interface reaction between the matrix and the carbon fiber occurs to form aluminum carbide (Al 4 C 3 ) and thereby decrease not only the cross section of the carbon fiber but also the strength of the carbon fiber due to the occurrence of a notch effect at the carbide end when the heating retention time becomes higher than or equal to 550°C.
  • Al 4 C 3 aluminum carbide
  • the present invention has been made to provide a nanocarbon/aluminum composite material having high strength and electrical conductivity for suitable use in electric conductors such as power cables and lead wires, heat exchangers such as radiators, condensers and evaporators and automotive parts, a process for production of the nanocarbon/aluminum composite material and a plating liquid for use in the nanocarbon/aluminum composite production process.
  • an room-temperature molten salt also called “cold molten salt”, “ambient-temperature molten salt” or “ionic liquid”
  • ionic liquid an room-temperature molten salt
  • the present inventors have proceeded with further researches and found that the above object of the present invention can be accomplished by preparing and using a specific plating liquid.
  • a plating liquid for nanocarbon/aluminum composite production comprising an aluminum halide, nanocarbon and 1,3-dialkylimidazolium halide and/or monoalkylpyridinium halide, wherein the molar ratio of the aluminum halide to the 1,3-dialkylimidazolium halide and/or the monoalkylpyridinium halide is in the range of 20 : 80 to 80 : 20; the 1,3-dialkylimidazolium halide has an alkyl group with a carbon number of 1 to 12; and the monoalkylpyridinium halide has an alkyl group with a carbon number 1 to 12
  • a first process for preparing the plating liquid for nanocarbon/aluminum composite production comprising: mixing aluminum halide and nanocarbon together, mixing the mixture of the aluminum halide and the nanocarbon with 1,3-dialkylimidazolium halide and/or monoalkylpyridinium halide, and then, melting the mixture of the aluminum halide, the nanocarbon and the 1,3-dialkylimidazolium halide and/or the monoalkylpyridinium halide; or mixing nanocarbon with 1,3-dialkylimidazolium halide and/or monoalkylpyridinium halide, mixing the mixture of the nanocarbon and the 1,3-dialkylimidazolium halide and/or the monoalkylpyridinium halide with aluminum halide, and then, melting the mixture of the aluminum halide, the nanocarbon and the 1,3-dialkylimidazolium halide and/or the monoalkylpyridinium halide with aluminum hal
  • a second process for preparing the plating liquid for nanocarbon/aluminum composite production comprising: mixing aluminum halide and nanocarbon together or mixing nanocarbon with 1,3-dialkylimidazolium halide and/or monoalkylpyridinium halide, and then, mixing the nanocarbon mixture with a molten salt of aluminum halide and 1,3-dialkylimidazolium halide and/or monoalkylpyridinium halide.
  • a process for producing a nanocarbon/aluminum composite material by using the plating liquid for nanocarbon/aluminum composite production according to the present invention comprising: forming a plating film on a substrate surface by electrolysis of the plating liquid in a dry, oxygen-free atmosphere with the passage of a direct current and/or a pulsed current under the electrolysis conditions of a bath temperature of 0 to 300°C and a current density of 0.01 to 50 A/dm 2 .
  • nanocarbon/aluminum composite material produced by the nanocarbon/aluminum composite production process according to the present invention.
  • nanocarbon/aluminum composite material having high strength and electrical conductivity for suitable use in electric conductors such power cables and lead wires, heat exchangers such as radiators, condensers and evaporators and automotive parts and a process for production of the nanocarbon/aluminum composite material by the preparation and use of a specific plating liquid.
  • the plating liquid for nanocarbon/aluminum composite production contains an aluminum halide, nanocarbon and either one or both of 1,3-dialkylimidazolium halide and monoalkylpyridinium halide, wherein the molar ratio of the aluminum halide to the 1,3-dialkylimidazolium halide and/or the monoalkylpyridinium halide is in the range of 20 : 80 to 80 : 20; the 1,3-dialkylimidazolium halide has an alkyl group or groups with a carbon number of 1 to 12; and the monoalkylpyridinium halide has an alkyl group with a carbon number of 1 to 12 as mentioned above.
  • the molar ratio of the aluminum halide to the 1,3-dialkylimidazolium halide and/or the monoalkylpyridinium halide is in the range of 20 : 80 to 80 : 20. If the above molar ratio is not satisfied, the resulting liquid does not get molten at room temperature and thus cannot be used as the plating liquid. Even when molten at higher temperature, the resulting liquid is too high in viscosity and not suitable as the plating liquid for production of the nanocarbon/aluminum composite material with high strength and electrical conductivity.
  • the 1,3-dialkylimidazolium halide and the monoalkylpyridinium halide can be used alone or in combination thereof as long as the above mole ratio condition is satisfied.
  • the 1,3-dialkylimidazolium halide has an alkyl group with a carbon number of 1 to 12; and the monoalkylpyridinium halide has an alkyl group with a carbon number of 1 to 12. If the alkyl group does not have the above carbon number, the resulting liquid does not get molten at room temperature and thus cannot be used as the plating liquid. Even when molten at higher temperature, the resulting liquid is too high in viscosity and not suitable as the plating liquid for production of the nanocarbon/aluminum composite material with high strength and electrical conductivity.
  • the plating liquid is capable of being used to produce the nanocarbon/aluminum composite material with high strength and electrical conductivity.
  • the nanocarbon is contained in an amount of 0.01 to 50 g/L, more preferably 0.01 to 20 g/L, with respect to the total volume of the aluminum halide and the 1,3-dialkylimidazolium halide and/or the monoalkylpyridinium halide. If the nanocarbon content amount is less than 0.01 g/L, the amount of nanocarbon particles in aluminum plating is so small that it may become difficult for the plating to obtain desired properties.
  • the concentration of nanocarbon particles in the electrolytic bath is so high that the nanocarbon particles may get aggregated and precipitated and, at the time of raising the product from the electrolytic bath upon completion of the electrolysis, adhered excessively to the product.
  • aluminum halide is preferably usable. It is particularly preferable to use anhydrous AlCl 3 .
  • the 1,3-dialkylimidazolium halide has at least one alkyl group with a carbon number of 1 to 12 and is capable of being used in the above plating liquid for production of the nanocarbon/aluminum composite material. It is preferable that the 1,3-dialkylimidazolium halide has one alkyl group with a carbon number of 1 to 5, more preferably two alkyl groups with a carbon number of 1 to 5. More specifically, 1-ethyl-3-methylimidazolium chloride (hereinafter referred to as "EMIC”) is preferably usable. These two alkyl groups may be the same or different.
  • EMIC 1-ethyl-3-methylimidazolium chloride
  • the monoalkylpyridinium halide has an alkyl group with a carbon number of 1 to 12 and is capable of being used in the above plating liquid for production of the nanocarbon/aluminum composite material. It is preferable that the monoalkylpyridinium halide has one alkyl group with a carbon number of 1 to 5. More specifically, 1-butylpyridinium halide (hereinafter referred to as "BPC") is preferably usable.
  • BPC 1-butylpyridinium halide
  • the EMIC having a low melting point of about 84°C.
  • nanocarbon there is no particular restriction on the nanocarbon.
  • the nanocarbon there can be used carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene, carbon black, acetylene black, ketjen black or any mixture thereof.
  • carbon nanotube with a diameter of 1 to 100 nm, a length of 1 to 100 ⁇ m and an aspect ratio of 10 to 100. If the carbon nanotube diameter is smaller than 1 nm, it is likely that the carbon nanotube will get aggregated and precipitated so that it is difficult to incorporate a sufficient amount of carbon nanotube in aluminum plating. If the carbon nanotube diameter exceeds 100 nm, it is also likely that the carbon nanotube will get precipitated so that it is difficult to incorporate a sufficient amount of carbon nanotube in aluminum plating.
  • the carbon nanotube length is less than 1 ⁇ m, it is likely that the carbon nanotube will get aggregated and precipitated so that it is difficult to incorporate a sufficient amount of carbon nanotube in aluminum plating as in the case where the carbon nanotube diameter is smaller than 1 nm. If the carbon nanotube length exceeds 100 ⁇ m, it is also likely that the carbon nanotube will get precipitated so that it is difficult to incorporate a sufficient amount of carbon nanotube in aluminum plating as in the case where the carbon nanotube diameter exceeds 100 nm.
  • the carbon nanotube may have either a single-wall structure, a multi-wall structure or any composite structure thereof.
  • a first process of preparing the plating liquid for nanocarbon/aluminum composite production according to the present invention includes mixing an aluminum halide and nanocarbon together, mixing the resulting mixture with either one or both of 1,3-dialkylimidazolium halide and monoalkylpyridinium halide and melting the mixture, or mixing a nanocarbon with either one or both of 1,3-dialkylimidazolium halide and monoalkylpyridinium halide, mixing the resulting mixture with an aluminum halide and melting the mixture.
  • a second process of preparing the plating liquid for nanocarbon/aluminum composite production according to the present invention includes mixing an aluminum halide and nanocarbon together, or mixing nanocarbon with either one or both of 1,3-dialkylimidazolium halide and monoalkylpyridinium halide, and then, mixing the resulting mixture with a molten salt of the aluminum halide and either one or both of 1,3-dialkylimidazolium halide and monoalkylpyridinium halide.
  • both of the 1,3-dialkylimidazolium halide and the monoalkylpyridinium halide have alkyl groups with a carbon number of 1 to 12, which may be the same or different.
  • the aluminum halide and the nanocarbon Any of the above-mentioned aluminum halide and nanocarbon materials are usable.
  • the plating liquid for nanocarbon/aluminum composite production according to the present invention is not limited to those prepared by the above first and second preparation processes and can be prepared by any process as long as the plating liquid has a specific composition of aluminum halide, nanocarbon and either one or both of 1,3-dialkylimidazolium halide and monoalkylpyridinium halide.
  • the nanocarbon is mixed in advance with the salt. This makes the nanocarbon unlikely to get aggregated and thus desirably leads to a uniform dispersion of the nanocarbon in the plating liquid.
  • the nanocarbon mixture is directly added into the molten salt of the aluminum halide and the 1,3-dialkylimidazolium halide and/or the monoalkylpyridinium halide. This promotes a desirably more uniform dispersion of the nanocarbon in the plating liquid.
  • the plating liquid can be prepared by e.g. mixing AlCl 3 as one kind of aluminum halide and EMIC as one kind of 1,3-dialkylimidazolium halide at a given molar ratio to obtain a room-temperature molten salt as a base, followed by adding thereto CNT as one kind of nanocarbon appropriately.
  • CNT as one kind of nanocarbon appropriately.
  • the room-temperature molten salt is not in a completely molten state, it is preferable to melt the salt completely by heating.
  • an Al wire in the completely molten salt before adding the CNT to the molten salt in order to remove impurities from the AlCl 3 -EMIC room-temperature molten salt.
  • the technique for dispersing the CNT in the AlCl 3 -EMIC room-temperature molten salt For example, ultrasonic irradiation or stirring can be used.
  • a process for producing the nanocarbon/aluminum composite material by using the plating liquid for nanocarbon/aluminum composite production according to the present invention includes forming a plating film on a substrate surface by electrolysis of the plating liquid in a dry, oxygen-free atmosphere with the passage of either a direct current, a pulsed current or an appropriate combination thereof under the electrolysis conditions of a bath temperature of 0 to 300°C and a current density of 0.01 to 50 A/dm 2 .
  • the plating liquid gets solidified. If the bath temperature exceeds 300°C, the plating liquid gets decomposed by heat. In either case, it is difficult to accomplish the electrolysis. If the current density is less than 0.01 A/dm 2 , the electrolysis time becomes too long for practical use. If the current density exceeds 50 A/dm 2 , the plating liquid reaches a decomposition voltage level so that it is difficult to accomplish the plating.
  • the "dry, oxygen-free atmosphere” means an atmosphere with a moisture content of 2 ppm or lower and an oxygen content of 1 ppm or lower in the present invention. An argon (Ar) or nitrogen (N 2 ) atmosphere is generally usable as the dry, oxygen-free atmosphere.
  • the nanocarbon/aluminum composite material (plating film) with high strength and electrical conductivity on the substrate surface. It is also possible by means of electroplating in the above process to form the plating film of the nanocarbon/aluminum composite material easily in a single process step. Further, the plating film of the nanocarbon/aluminum composite material can be formed into a desired shape.
  • the electrolysis can be accomplished by using any known two-electrode cell.
  • One example of the electrolysis is to apply a voltage to the plating liquid, in which the CNT is dispersed in the AlCl 3 -EMIC room-temperature molten salt, with a cathode and an anode immersed in the plating liquid and connected to a direct-current power source to feed a constant current, a pulsed current or a combination thereof between these two electrodes.
  • the intensity of the applied voltage may be changed at each period.
  • the electrolysis may be done intermittently for about 0.1 to 600 seconds.
  • the electrolysis may be done by repeated cycles of voltage application and stop as necessary at intervals of about 0.1 to 1 second.
  • the plating amount of the nanocarbon/aluminum composite material can be controlled by adjusting the nanocarbon dispersion amount, the current density, the electrolysis time and the like as appropriate.
  • the plating amount of the nanocarbon/aluminum composite material can be increased by increasing the nanocarbon dispersion amount, raising the electrolysis voltage to increase the current density, increasing the electrolysis time or any combination thereof.
  • the cathode can be an electric conductor of any material and form as long as it is chemically and electrochemically stable toward the plating liquid.
  • the cathode material there can be used e.g. copper, brass, nickel, stainless, tungsten, molybdenum and the like. Copper and brass are preferred in terms of the electrochemical stability, drawability and cost efficiency, but are not limited thereto.
  • the cathode form the surface configuration, thickness and size are not particularly restricted.
  • the cathode can be a porous metal substrate of foil form, plate form, spiral wire form, foam form, nonwoven form, mesh form, felt form or expanded form. Among others, foil form and plate form are preferred.
  • any known conductive substrate can be used with no particular restriction.
  • the anode material can be preferably selected from platinum and graphite that are chemically and electrochemically stable toward the plating liquid, and aluminum that does not cause contamination of the plating liquid by dissolution. There is no particular restriction on the form of the anode.
  • the anode can be of e.g. plate form or spiral form.
  • the nanocarbon/aluminum composite material is produced by the above nanocarbon/aluminum composite production process.
  • the thus-produced nanocarbon/aluminum composite material is capable of not only attaining high electrical and thermal conductivity but also being provided in thinner form for weight and size reduction and thus is suitable as a high-strength lightweight composite material for use in power cables, lead wires, heat exchangers such as radiators, condensers and evaporators, automotive parts and the like.
  • the plating film of the nanocarbon/aluminum composite material can be formed by the above electrolystic technique.
  • the nanocarbon content of the nanocarbon/aluminum composite material is preferably in the range of 0.1 to 50%, more preferably 0.1 to 20%. If the nanocarbon content is less than 0.1%, the material cannot obtain desired properties with almost none of nanocarbon characteristic features reflected therein. If the nanocarbon content exceeds 50%, the aluminum content is too low to function as a matrix for establishing a bonding between the nanocarbon particles so that the nanocarbon-to-nanocarbon bonding may become weakened to cause a sudden deterioration of material strength.
  • a plating liquid for MWCNT/aluminum composite production was prepared by adding 0.1 to 30.0 g/L of multi-wall carbon nanotube (MWCNT with a tube diameter of 1.2 to 2.0 nm and a tube length of 2 to 5 ⁇ m) into the above mixture.
  • MWCNT multi-wall carbon nanotube
  • a NWCNT/aluminum composite material was then produced by constant current electrolysis of the plating liquid with sufficient stirring.
  • the preparation and electrolysis of the plating liquid were carried out in a dry nitrogen atmosphere.
  • a two-electrode cell with a cathode of Cu plate (99.96%) and an anode of Al plate (99.99%) was used.
  • the cathode had been pretreated by grinding with an emery paper (No. 2000), electrolytic degreasing with 10% aqueous solution of sodium orthosilicate and then acid treatment with 10 vol% HCl.
  • the electrolysis conditions were set to a bath temperature of 30°C, a current density of 5,10, 20, 30 mA/cm 2 and an electrolysis charge amount of 50 C/cm 2 .
  • a surface state of the NWCNT/aluminum composite material was monitored by means of a scanning electron microscope (SEM "JSM-6500F” available from JEOL Ltd.) so as to observe the incorporation of NWCNT into the Al deposit in a practical manner.
  • SEM scanning electron microscope
  • the observation showed that the NWCNT was first adsorbed onto deposit surfaces, then captured by initial Al deposit nucleus (about 1 to 100,000 atoms), totally incorporated into the grown Al deposit nucleus and then almost completely embedded in the Al deposit. It has been found out by the observation that the NWCNT was eutectic with Al and present in monodisperse form.
  • the MWCNT content of the MWCNT/aluminum composite material was determined to be 0.1 to 20% by means of a total organic carbon meter ("TOC-5000A" available from SHIMADZU Corporation).
  • TOC-5000A total organic carbon meter
  • the relationship between the MNCNT addition amount of the plating liquid and the Vickers hardness of the composite material was analyzed as follows. (Refer to FIG. 1 .) The analysis was made semiquantitatively on the assumptions that an increase in the MWCNT eutectic amount could allow an increase in the composite material hardness and that the hardness of an Al plating film with an MWCNT addition amount of 0 g/L was adopted as a comparative example.
  • the hardness of the Al plating film was 50 Hv when the current density was set to any of 50, 10, 20 and 30 mA/cm 2 .
  • the hardness of the composite material became higher than that of the Al plating film at each current density as the MWCNT addition amount of the plating bath increased.
  • the eutectic of the MWCNT was supported by the increased hardness of the composite material in the present example.
  • a Vickers hardness tester (“HM-124" available from AKASHI Co. Ltd.) was used in the hardness measurement.
  • the specific resistance of the composite material was further determined by four-terminal measurement according to JIS C 2525 and found to be lower than that of the Al plating film. Based on the above results, analyses were also made on other kinds of nanocarbon particles. The same effect was obtained by the use of any of single-wall carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene, carbon black, acetylene black and ketjen black. The usability of the nanocarbon/aluminum composite material, composite production method and plating liquid according to the present invention have thus been proved as above.
  • a predetermined amount of EMIC and MWCNT (with a tube diameter of 1.2 to 2.0 nm and a tube length of 2 to 5 ⁇ m) was mixed together, followed by adding AlCl 3 and melting the resulting mixture to yield a plating liquid for MWCNT/aluminum composite production.
  • the molar ratio of AlCl 3 and EMIC in the plating liquid was set to 66.7 : 33.3.
  • the MWCNT addition amount was set to 0.1 to 30.0 g/L.
  • ANWCNT/aluminum composite material was then produced by constant current electrolysis of the plating liquid with sufficient stirring as is the case with Example 1.
  • the preparation and electrolysis of the plating liquid were herein carried out in a dry nitrogen atmosphere. Further, the two-electrode electrolysis cell, the cathode pretreatment process and the electrolysis conditions were the same as in Example 1.
  • a surface state of the NWCNT/aluminum composite material was observed by means of SEM. It has been found out by the observation that the NWCNT was eutectic with Al and present in monodisperse form as is the case with Example 1.
  • the MWCNT content of the MWCNT/aluminum composite material was determined to be 0.1 to 20% by means of a total organic carbon meter ("TOC-5000A" available from SHIMADZU Corporation).
  • TOC-5000A total organic carbon meter
  • the relationship between the MNCNT addition amount of the plating liquid and the Vickers hardness of the composite material was analyzed as follows. (Refer to FIG. 2 .) As is the case with Example 1, the analysis was made on the assumption that the hardness of an Al plating film with an MWCNT addition amount of 0 g/L was adopted as a comparative example. The hardness of the composite material became higher than that of the Al plating film at each current density as the MWCNT addition amount of the plating bath increased As shown in FIG. 2 .
  • the eutectic of the MWCNT was supported by the increased hardness of the composite material in the present example.
  • a Vickers hardness tester (“HM-124" available from AKASHI Co. Ltd.) was used in the hardness measurement.
  • the specific resistance of the composite material was further determined by four-terminal measurement and found to be lower than that of the Al plating film. Based on the above results, analyses were also made on other kinds of nanocarbon particles. The same effect was obtained by the use of any of single-wall carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene, carbon black, acetylene black and ketjen black. The usability of the nanocarbon/aluminum composite material, composite production method and plating liquid according to the present invention have thus been proved as above.
  • a predetermined amount of EMIC and MWCNT (with a tube diameter of 1.2 to 2.0 nm and a tube length of 2 to 5 ⁇ m) was mixed together and added to an AlCl 3 -EMIC molten salt to yield a plating liquid for MWCNT/aluminum composite production.
  • the molar ratio of AlCl 3 and EMIC in the plating liquid was set to 66.7 : 33.3.
  • the MWCNT addition amount was set to 0.1 to 30.0 g/L.
  • a NWCNT/aluminum composite material was then produced by constant current electrolysis of the plating liquid with sufficient stirring as is the case with Example 1.
  • the preparation and electrolysis of the plating liquid were herein carried out in a dry nitrogen atmosphere. Further, the two-electrode electrolysis cell, the cathode pretreatment process and the electrolysis conditions were the same as in Example 1.
  • a surface state of the NWCNT/aluminum composite material was observed by means of SEM. It has been found out by the observation that the NWCNT was eutectic with Al and present in monodisperse form as is the case with Example 1.
  • the MWCNT content of the MWCNT/aluminum composite material was determined to be 0.1 to 20% by means of a total organic carbon meter ("TOC-5000A" available from SHIMADZU Corporation).
  • TOC-5000A total organic carbon meter
  • the relationship between the MNCNT addition amount of the plating liquid and the Vickers hardness of the composite material was analyzed as follows. (Refer to FIG. 3 .) As is the case with Example 1, the analysis was made on the assumption that the hardness of an Al plating film with an MWCNT addition amount of 0 g/L was adopted as a comparative example. The hardness of the composite material became higher than that of the Al plating film at each current density as the MWCNT addition amount of the plating bath increased As shown in FIG. 3 .
  • the eutectic of the MWCNT was supported by the increased hardness of the composite material in the present example.
  • a Vickers hardness tester (“HM-124" available from AKASHI Co. Ltd.) was used in the hardness measurement.
  • the specific resistance of the composite material was further determined by four-terminal measurement and found to be lower than that of the Al plating film. Based on the above results, analyses were also made on other kinds of nanocarbon particles. The same effect was obtained by the use of any of single-wall carbon nanotube, carbon nanofiber, carbon nanohorn, fullerene, carbon black, acetylene black and ketjen black. The usability of the nanocarbon/aluminum composite material, composite production method and plating liquid according to the present invention have thus been proved as above.
EP06766838A 2005-09-07 2006-06-16 Nanocarbon/aluminum composite material, process for producing the same, and plating liquid for use in said process Withdrawn EP1930481A1 (en)

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JP2005258646A JP2007070689A (ja) 2005-09-07 2005-09-07 ナノカーボン／アルミニウム複合材、その製造方法及びこれに用いるめっき液
PCT/JP2006/312152 WO2007029395A1 (ja) 2005-09-07 2006-06-16 ナノカーボン／アルミニウム複合材、その製造方法及びこれに用いるめっき液

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CN (1) CN101258269A (zh)
WO (1) WO2007029395A1 (zh)

Cited By (4)

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WO2009019147A3 (en) * 2007-08-06 2009-11-12 Katholieke Universiteit Leuven Deposition from ionic liquids
EP2280095A3 (de) * 2009-07-30 2013-07-24 Ewald Dörken Ag Verfahren zur elektrochemischen Beschichtung eines Werkstücks
EP2500969A4 (en) * 2009-11-11 2016-01-06 Hitachi Metals Ltd ALUMINUM SHEET SUPPORTING CARBON PARTICLES DIFFUSED ON IT
EP2971268A1 (en) * 2013-03-12 2016-01-20 Ucciardello, Nadia Electrodeposition on metal foams

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4955268B2 (ja) * 2005-12-28 2012-06-20 東京特殊電線株式会社 フラーレン複合めっき電線及びその製造方法並びにフラーレン複合めっきエナメル電線
KR100907804B1 (ko) * 2007-04-26 2009-07-16 주식회사 대유신소재 전기 도금을 이용한 탄소 재료의 알루미늄 도금 장치 및 방법
KR100906746B1 (ko) 2007-12-21 2009-07-09 성균관대학교산학협력단 탄소재료를 알루미늄 속에 캡슐화하는 방법
KR100907334B1 (ko) * 2008-01-04 2009-07-13 성균관대학교산학협력단 알루미늄과 탄소재료 간의 공유결합을 형성하는 방법, 알루미늄과 탄소재료 복합체를 제조하는 방법 및 그 방법에 의하여 제조된 알루미늄과 탄소재료 복합체
CN102041543B (zh) * 2009-10-20 2012-10-10 宝山钢铁股份有限公司 金属表面富勒烯/金属复合薄膜的制备方法
CN103298981A (zh) 2010-12-28 2013-09-11 独立行政法人产业技术综合研究所 Cnt金属复合材料及其制造方法
WO2015012275A1 (ja) 2013-07-22 2015-01-29 独立行政法人産業技術総合研究所 Ｃｎｔ金属複合材及びその製造方法
US20160108534A1 (en) * 2014-10-17 2016-04-21 Ut-Battelle, Llc Aluminum deposition devices and their use in spot electroplating of aluminum
CN104726924A (zh) * 2015-03-25 2015-06-24 西南石油大学 一种镍钨多壁碳纳米管复合镀液、镀膜及其制备方法
CN107164660A (zh) * 2017-04-18 2017-09-15 中北大学 一种C60增强Al基复合材料及其制备方法
CN107313102B (zh) * 2017-07-03 2019-02-26 鄂尔多斯市紫荆创新研究院 一种铝基石墨烯、碳纳米管复合散热材料的制备方法
US11512390B2 (en) 2018-07-16 2022-11-29 Rochester Institute Of Technology Method of site-specific deposition onto a free-standing carbon article
US20210156041A1 (en) * 2019-11-22 2021-05-27 Hamilton Sundstrand Corporation Metallic coating and method of application

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0445298A (ja) * 1990-06-11 1992-02-14 Nisshin Steel Co Ltd 電気アルミニウムめっき浴
JP2004076031A (ja) * 2002-08-09 2004-03-11 Ishikawajima Harima Heavy Ind Co Ltd 電解めっき用めっき浴及び複合めっき用めっき浴並びにこれらの製造方法
JP4032116B2 (ja) * 2002-11-01 2008-01-16 国立大学法人信州大学 電子部品およびその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007029395A1 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009019147A3 (en) * 2007-08-06 2009-11-12 Katholieke Universiteit Leuven Deposition from ionic liquids
EP2280095A3 (de) * 2009-07-30 2013-07-24 Ewald Dörken Ag Verfahren zur elektrochemischen Beschichtung eines Werkstücks
EP2500969A4 (en) * 2009-11-11 2016-01-06 Hitachi Metals Ltd ALUMINUM SHEET SUPPORTING CARBON PARTICLES DIFFUSED ON IT
EP2971268A1 (en) * 2013-03-12 2016-01-20 Ucciardello, Nadia Electrodeposition on metal foams

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