CN101258269A - 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 PDFInfo
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- CN101258269A CN101258269A CNA2006800328310A CN200680032831A CN101258269A CN 101258269 A CN101258269 A CN 101258269A CN A2006800328310 A CNA2006800328310 A CN A2006800328310A CN 200680032831 A CN200680032831 A CN 200680032831A CN 101258269 A CN101258269 A CN 101258269A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 129
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 238000007747 plating Methods 0.000 title claims abstract description 78
- 239000007788 liquid Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910021392 nanocarbon Inorganic materials 0.000 title abstract description 15
- 230000008569 process Effects 0.000 title abstract description 5
- -1 aluminum halide Chemical class 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 166
- 229910052799 carbon Inorganic materials 0.000 claims description 141
- 239000002105 nanoparticle Substances 0.000 claims description 121
- 230000026030 halogenation Effects 0.000 claims description 78
- 238000005658 halogenation reaction Methods 0.000 claims description 78
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 76
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 22
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- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 19
- 230000004927 fusion Effects 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002116 nanohorn Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 150000004820 halides Chemical class 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000002048 multi walled nanotube Substances 0.000 description 25
- 239000011159 matrix material Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- 239000000374 eutectic mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005269 aluminizing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000006200 vaporizer Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000007542 hardness measurement Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- TWHBEKGYWPPYQL-UHFFFAOYSA-N aluminium carbide Chemical compound [C-4].[C-4].[C-4].[Al+3].[Al+3].[Al+3].[Al+3] TWHBEKGYWPPYQL-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- 230000002787 reinforcement Effects 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000013585 weight reducing agent 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
- 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
Abstract
The present invention provides a nanocarbon/aluminum composite material having both high strength and electrical conductivity, which is suitable for use in lead wires, heat exchangers, and automobile components, and a process for producing the same. A plating liquid for nanocarbon/aluminum composite material formation, comprising an aluminum halide, nanocarbon, a 1,3-dialkylimidazolium halide and the like, wherein the molar ratio of the aluminum halide to the 1,3-dialkylimidazolium halide and the like is 20:80 to 80:20. The 1,3-dialkylimidazolium halide and the like contain an alkyl group having 1 to 12 carbon atoms. In the production process of a nanocarbon/aluminum composite material, the surface of a base material is plated in a dry oxygen-free atmosphere using the plating liquid for nanocarbon/aluminum composite material formation, for example, by direct current under electrolysis conditions of bath temperature 0 to 300 C and current density 0.01 to 50 A/dm<2>. There is also provided a nanocarbon/aluminum composite material produced by the production process.
Description
Technical field
The present invention relates to following: nano-sized carbon/aluminum composite, this matrix material are specially adapted to electric conductor such as power cable and lead-in wire, heat exchanger such as scatterer, condenser and vaporizer and trolley part; The plating liquid that is used for producing the method for this nano-sized carbon/aluminum composite and is used for described nano-sized carbon/aluminum composite production method.
Background technology
Usually, require power cable and lead material such as aluminium alloy and heat exchanger material to have high conductivity and high thermal conductivity.
Based on recent global environmental protection viewpoint, there is growing demand in the weight and the compact in size of power cable, lead-in wire, heat exchanger and trolley part.Thereby expectation power cable, lead-in wire, heat exchanger and trolley part material have high strength, simultaneously with thinner form moulding.
The carbon fiber reinforcement aluminium alloy as the high strength low weight composites has been carried out a large amount of research (referring to patent document 1 and 2) up to now.
Simultaneously, also caused people's attention recently as the carbon nanotube of carbon fiber (below be called " CNT ").Because good character such as toughness, electroconductibility and the thermal conductivity of CNT is in the suitability of having studied CNT aspect the prospect of further improvement in performance.
Can use various metals such as copper, nickel and aluminium as the matrix (referring to patent document 3 and 4) that is used to produce the CNT matrix material.Especially, reported that intensity improves and obtained the CNT/ aluminum composite (referring to non-patent document 1) of high thermal conductivity.
On the other hand, known various aluminum production method is as three layers of electrolysis, fractional crystallization and galvanic deposit.Wherein, electro-deposition method carries out with one step, thereby is considered to the most attractive.Yet because aluminium has the fact with respect to the negative Standard Electrode Potentials of SHE (standard hydrogen electrode)-1.68V, under the influence of competitive hydrogen formation reaction, galvanic deposit is unpractical from aqueous systems.Though can from organic solvent system, galvanic deposit be difficult to it is committed to industrial practical application still owing to the danger of flash burn (flashing).
Patent document 1: the Japanese Patent spy opens 2005-008989 number
Patent document 2: the Japanese Patent spy opens 2005-048206 number
Patent document 3: the Japanese Patent spy opens 2004-156074 number
Patent document 4: the Japanese Patent spy opens 2004-315297 number
Non-patent document 1:Journal of Materials Research, T.Kuzamaki et al., 1998, Vol.13, P.2445.
Summary of the invention
Technical problem to be solved by this invention
Every kind of method steps that includes a series of complexity of the nano-sized carbon of patent document 1-4 and non-patent document 1/aluminum composite production method, as aluminium powder and CNT are placed aluminum container, subsequently under 600 ℃ in 5.310
-1Down heating 1.5 hours of the decompression of Pa, pressurization is 60 minutes under 100MPa, extrudes under 10MPa/min and 600 ℃ then.In these production methods, add and nano-sized carbon is mixed in the molten metal by stirring.Thereby produced because the bigger difference of proportion between metal and nano-sized carbon, be difficult to make nano-sized carbon to be evenly dispersed in problem in the molten metal.
Carbon fiber/aluminum composite when in non-oxidizing atmosphere in 500 ℃ or when more heating under the low temperature, do not show the strength degradation phenomenon.Yet, when heating keeps temperature to be greater than or equal to 550 ℃, in this carbon fiber/aluminum composite, produced and between matrix and carbon fiber, surface reaction taken place and generate aluminium carbide (Al
4C
3) problem, thereby owing to, this carbon fiber cross section is reduced, but also fibre strength is descended in the appearance of the terminal notch effect of this carbide.
Research formerly shows that also carbon fiber is oxidized by heating in air, thereby is faced with the serious problems of deterioration.
Based on above-mentioned prior art problems, carry out the present invention with provide have high strength and electroconductibility be applicable to electric conductor such as power cable and lead-in wire, the nano-sized carbon/aluminum composite of heat exchanger such as scatterer, condenser and vaporizer and trolley part; The plating liquid that is used to produce the method for this nano-sized carbon/aluminum composite and is used for this nano-sized carbon/aluminum composite production method.
The means of dealing with problems
Result as big quantity research, the inventor has proposed a scientific discovery, expects that promptly room temperature melting salt (being also referred to as " cold melting salt ", " envrionment temperature melting salt " or " ionic liquid ") is owing to following advantage (1)-(3) are specially adapted to various alloy electroplating baths and electrolytic tank electrolysis matter.
(1) the room temperature melting salt can make any metal or alloy as aluminium with negative Standard Electrode Potentials plating easily.
(2) the room temperature melting salt can at room temperature use, and easy handling.
(3) the room temperature melting salt shows non-volatile and non-flammable, does not have the danger of flash burn.
Based on this scientific discovery, the inventor makes further research, and finds that above-mentioned purpose of the present invention can be by preparing and using specific plating liquid to realize.
Promptly, the plating liquid that is used for according to nano-sized carbon of the present invention/aluminum composite production is provided, it comprises aluminum halide, nano-sized carbon and halogenation 1,3-dialkylimidazolium and/or halogenation monoalkyl pyridine, wherein aluminum halide and halogenation 1, the mol ratio of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine is 20: 80-80: in 20 scopes; Described halogenation 1, the 3-dialkylimidazolium has the alkyl of carbon number 1-12; And described halogenation monoalkyl pyridine has the alkyl of carbon number 1-12.
Provide and prepared the first method that is used for according to the plating liquid of nano-sized carbon of the present invention/aluminum composite production, it comprises: aluminum halide and nano-sized carbon are mixed, mixture and halogenation 1 with this aluminum halide and nano-sized carbon, 3-dialkylimidazolium and/or halogenation monoalkyl pyridine mix, this aluminum halide of fusion, nano-sized carbon and halogenation 1 then, the mixture of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine; Or with nano-sized carbon and halogenation 1,3-dialkylimidazolium and/or halogenation monoalkyl pyridine mix, with this nano-sized carbon and halogenation 1, the mixture of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine mixes with aluminum halide, then, this aluminum halide of fusion, nano-sized carbon and halogenation 1, the mixture of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine.
Provide and prepared the second method that is used for according to the plating liquid of nano-sized carbon of the present invention/aluminum composite production, it comprises: aluminum halide and nano-sized carbon are mixed, or with nano-sized carbon and halogenation 1,3-dialkylimidazolium and/or halogenation monoalkyl pyridine mix, with this nano-sized carbon mixture and aluminum halide and halogenation 1, the melting salt of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine mixes then.
The method that is used for plating liquid production nano-sized carbon/aluminum composite of producing according to nano-sized carbon of the present invention/aluminum composite by use also is provided, and it comprises: by bathe gentle 0.01-50A/dm at 0-300 ℃ in dry oxygen-free atmosphere
2The electrolytic condition of current density feeds direct current and/or this plating liquid of pulsed current electrolysis down and form plated film on substrate surface.
Nano-sized carbon/aluminum composite of producing by nano-sized carbon according to the present invention/aluminum composite production method further is provided.
The invention effect
Can provide in the present invention have high strength and electroconductibility be applicable to electric conductor such as power cable and lead-in wire, the nano-sized carbon/aluminum composite of heat exchanger such as scatterer, condenser and vaporizer and trolley part; With by the preparation and use specific plating liquid to produce the method for this nano-sized carbon/aluminum composite.
Description of drawings
Fig. 1 illustrates the figure that concerns between NWCNT add-on and material hardness in embodiment 1 and the comparative example.
Fig. 2 illustrates the figure that concerns between NWCNT add-on and material hardness in embodiment 2 and the comparative example.
Fig. 3 illustrates the figure that concerns between NWCNT add-on and material hardness in embodiment 3 and the comparative example.
Embodiment
Hereinafter detailed description is used for plating liquid according to nano-sized carbon of the present invention/aluminum composite production.In the following description, unless otherwise indicated, otherwise all percentage ratios (%) are mass percent.
Be used for comprising aluminum halide, nano-sized carbon and halogenation 1 according to the plating liquid of nano-sized carbon of the present invention/aluminum composite production, one of the two of 3-dialkylimidazolium and halogenation monoalkyl pyridine or two kinds, as mentioned above, wherein aluminum halide and halogenation 1, the mol ratio of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine is 20: 80-80: in 20 scopes; Described halogenation 1, the 3-dialkylimidazolium has the alkyl of carbon number 1-12; And described halogenation monoalkyl pyridine has the alkyl of carbon number 1-12.
In the present invention, aluminum halide and halogenation 1, the mol ratio of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine is 20: 80-80: be necessary in 20 scopes.
If above-mentioned mol ratio does not satisfy, the liquid that then obtains fusion at room temperature, thus can not be used as plating liquid.Even when fusion under higher temperature, the liquid viscosity that obtains is too high, also is not suitable as the plating liquid that is used to produce the nano-sized carbon/aluminum composite with high strength and electroconductibility.
Here, halogenation 1,3-dialkylimidazolium and halogenation monoalkyl pyridine can be used alone or in combination, as long as it satisfies above-mentioned mol ratio condition.
In the present invention, halogenation 1, the 3-dialkylimidazolium has the alkyl of carbon number 1-12; The alkyl that has carbon number 1-12 with halogenation monoalkyl pyridine also is necessary.
If described alkyl does not have above-mentioned carbon number, the liquid that then obtains fusion at room temperature, thus can not be used as described plating liquid.Even when fusion under higher temperature, the liquid viscosity that obtains is too high, is not suitable as the plating liquid that is used to produce the nano-sized carbon/aluminum composite with high strength and electroconductibility.
Yet, adopting above-mentioned composition, described plating liquid can be used in produces the nano-sized carbon/aluminum composite with high strength and electroconductibility.
In the present invention preferably with respect to aluminum halide and halogenation 1, the cumulative volume 0.01-50g/L of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine, more preferably the amount of 0.01-20g/L comprises described nano-sized carbon.
If nano-sized carbon contain quantity not sufficient 0.01g/L, then nano carbon particle is very few in aluminizing, to such an extent as to be difficult to the character that obtains to expect for described plating.If nano-sized carbon content surpasses 50g/L, then nano carbon particle excessive concentration in the electrolytic bath to such an extent as to nano carbon particle may also deposit in agglomeration, is finished thereby work as electrolysis, when from electrolytic bath, taking out product, and excessive sticking on the described product.
Below various liquid ingredients will be described in further detail.
To at first provide explanation below about aluminum halide.
Aluminum halide is not particularly limited, as long as it can be in the above-mentioned plating liquid use that is used for producing described nano-sized carbon/aluminum composite.For example, can preferably use aluminum chloride (AlCl
3).The anhydrous AlCl of preferred especially use
3
Next, will provide about halogenation 1 explanation of 3-dialkylimidazolium below.
To halogenation 1, the 3-dialkylimidazolium is not particularly limited, as long as it has the alkyl of at least one carbon number 1-12, and can use at the above-mentioned plating liquid that is used for producing described nano-sized carbon/aluminum composite and gets final product.Preferred halogenation 1, the 3-dialkylimidazolium has the alkyl of a carbon number 1-5, more preferably has the alkyl of two carbon number 1-5.More particularly, can preferably use chlorination 1-ethyl-3-Methylimidazole (below be called " EMIC ").These two alkyl can be identical or different.
Below provide explanation about halogenation monoalkyl pyridine.
Halogenation monoalkyl pyridine is not particularly limited,, and can uses at the above-mentioned plating liquid that is used for producing described nano-sized carbon/aluminum composite and get final product as long as it has the alkyl of carbon number 1-12.Preferred described halogenation monoalkyl pyridine has the alkyl of a carbon number 1-5.More particularly, can preferably use halogenation 1-butyl-pyridinium (below be called " BPC ").
At the physical properties of described plating liquid, particularly specific conductivity, viscosity and fusing point aspect, the preferred use has about 84 ℃ low-melting EMIC.
Below provide explanation about nano-sized carbon.
Nano-sized carbon is not particularly limited.As nano-sized carbon, can use carbon nanotube, carbon nanofiber, Carbon Nanohorn (nanohorn), soccerballene, carbon black, acetylene black, ketjen carbon black or its any mixture.
In the present invention, the preferred carbon nanotube that uses as a kind of nano-sized carbon with 1-100nm diameter, 1-100 μ m length and 10-100 length-to-diameter ratio.
If the diameter of described carbon nanotube is less than 1nm, then agglomeration and deposition may take place in carbon nanotube, to such an extent as to be difficult to mix the carbon nanotube of q.s in aluminizing.If the diameter of described carbon nanotube surpasses 100nm, then carbon nanotube may deposit equally, to such an extent as to be difficult to mix the carbon nanotube of q.s in aluminizing.If the curtailment of described carbon nanotube 1 μ m, then agglomeration and deposition may take place in carbon nanotube, to such an extent as to the carbon nanotube diameter the same carbon nanotube that is difficult in aluminizing, mix q.s during less than 1nm.If the length of described carbon nanotube surpasses 100 μ m, then carbon nanotube may deposit equally, to such an extent as to the same carbon nanotube that is difficult to mix q.s in aluminizing when surpassing 100nm with the carbon nanotube diameter.
Here, described carbon nanotube can have single-wall structure, many wall constructions or its composite structure arbitrarily.
Next, below explanation is used for the preparation of the plating liquid produced according to nano-sized carbon of the present invention/aluminum composite.
Preparation is used for first method according to the plating liquid of nano-sized carbon of the present invention/aluminum composite production and comprises aluminum halide and nano-sized carbon are mixed, with mixture and the halogenation 1 that obtains, 3-dialkylimidazolium and halogenation monoalkyl pyridine both one of or both mix and this mixture of fusion; Or with nano-sized carbon and halogenation 1,3-dialkylimidazolium and halogenation monoalkyl pyridine both one of or both mix, the mixture that obtains is mixed with aluminum halide, and this mixture of fusion.
Second method of plating liquid that preparation is used for nano-sized carbon of the present invention/aluminum composite production comprises aluminum halide and nano-sized carbon is mixed, or with nano-sized carbon and halogenation 1,3-dialkylimidazolium and halogenation monoalkyl pyridine both one of or both mix, then with the mixture and aluminum halide and the halogenation 1 that obtain, the melting salt of one of the two of 3-dialkylimidazolium and halogenation monoalkyl pyridine or two kinds mixes.
In first kind and second kind of preparation method, described halogenation 1,3-dialkylimidazolium and halogenation monoalkyl pyridine all have the alkyl of carbon number 1-12, and described alkyl can be identical or different.
Aluminum halide and nano-sized carbon are not particularly limited.Can use any above-mentioned aluminum halide and nano-carbon material.
Being used for plating liquid according to nano-sized carbon of the present invention/aluminum composite production is not limited to by those of above-mentioned first kind and second kind preparation method's preparation, can adopt any method preparation, as long as this plating liquid has aluminum halide, nano-sized carbon and halogenation 1, the specific composition of one of the two of 3-dialkylimidazolium and halogenation monoalkyl pyridine or two kinds gets final product.Under the situation of the plating liquid that is used for nano-sized carbon/aluminum composite production by first kind of preparation method preparation, nano-sized carbon is pre-mixed in described salt.This makes that nano-sized carbon can not agglomeration, thereby causes nano-sized carbon to be disperseed uniformly in plating liquid ideally.Under the situation of the plating liquid that is used for nano-sized carbon/aluminum composite production by the preparation of second preparation method, described nano-sized carbon mixture directly adds aluminum halide and halogenation 1, in the melting salt of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine.This has promoted nano-sized carbon to disperse more equably ideally in plating liquid.
As more concrete example, described plating liquid can be by for example will be as a kind of AlCl of aluminum halide
3With as a kind of halogenation 1, the EMIC of 3-dialkylimidazolium mixes under given mol ratio, to obtain the room temperature melting salt as matrix, prepares to the CNT that wherein adds aptly as a kind of nano-sized carbon then.
Be easy handling, preferably before CNT is added melting salt, CNT be dispersed in AlCl
3Or among the EMIC.
When described room temperature melting salt is not complete molten state, preferably melt this salt fully by heating.
Further preferably before CNT being added in this melting salt, aluminium wire is immersed in this complete fused salt, with from AlCl
3Remove impurity in the-EMIC room temperature melting salt.
To at this AlCl
3Disperse the technology of CNT to be not particularly limited in-EMIC room temperature the melting salt.For example can adopt ultrasonic radiation or stirring.
The production of described nano-sized carbon/aluminum composite will be described below.
By adopting the method that is used for the plating liquid production nano-sized carbon/aluminum composite of nano-sized carbon/aluminum composite production according to the present invention to comprise, bathe gentle 0.01-50A/dm at 0-300 ℃ by at dry oxygen-free atmosphere
2Under the electrolytic condition of current density, feed direct current, pulsed current or its suitable combination and come this plating liquid of electrolysis to form plated film at substrate surface.
Be lower than 0 ℃ if bathe temperature, then plating liquid can solidify.Surpass 300 ℃ if bathe temperature, then plating liquid can decomposes.In both cases, all be difficult to realize electrolysis.
If current density is lower than 0.01A/dm
2, then electrolysis time is long in the practical application.If current density surpasses 50A/dm
2, then plating liquid reaches the decomposition voltage level, to such an extent as to be difficult to realize plating.
Here, in the present invention, " dry oxygen-free atmosphere " is meant to have 2ppm or lower moisture content and 1ppm or the atmosphere of low oxygen content more.Argon gas (Ar) or nitrogen (N
2) can be used as this drying oxygen-free atmosphere usually.
By aforesaid method, can have the nano-sized carbon/aluminum composite (plated film) of high strength and electroconductibility in substrate surface production.
Also can in the single method step, easily form nano-sized carbon/aluminum composite plated film by the plating in aforesaid method.Further, this nano-sized carbon/aluminum composite plated film can form the shape of expectation.
Electrolysis tech in described nano-sized carbon/aluminum composite production is not particularly limited.For example, electrolysis can adopt any known dual-electrode electrolysis groove (two-electrodecell) to realize.
An electrolytic example is dispersed in AlCl for voltage is put on CNT
3In the plating liquid of-EMIC room temperature melting salt, wherein negative electrode and anode are immersed in the plating liquid and are connected to direct supply to supply with constant current, pulsed current or its combination between two electrodes.
The voltage strength that applies can change in each period.
Electrolysis can be intermittently about 0.1-600 second.
Electrolysis can be carried out with the recirculation that about 0.1-1 in case of necessity stops second at interval by applying voltage.
The plating amount of nano-sized carbon/aluminum composite can be by regulating controls such as nano-sized carbon dispersion amount, current density, electrolysis time aptly.
For example, the plating amount of nano-sized carbon/aluminum composite can increase to increase current density, increase electrolysis time or its arbitrary combination by increase nano-sized carbon dispersion amount, raising electrolysis voltage.
Under described nano-sized carbon/aluminum composite quantity-produced situation, it is desirable to continuous supplementation nano-sized carbon and AlCl
3-EMIC room temperature melting salt is to remedy the decline of nano-sized carbon dispersion amount.
The material and the form of anticathode (negative pole) are not particularly limited.This negative electrode can be the electric conductor of any material and form, as long as it is for plating liquid chemistry and electrochemical stability.
As cathode material, can use for example copper, brass, nickel, stainless steel, tungsten, molybdenum etc.According to electrochemical stability, tensility and cost efficiency, preferably copper and brass, but be not limited only to this.
As the form of negative electrode, surfac topography, thickness and size are not particularly limited.This negative electrode can be the porous metallic substrate of foil-shaped, plate shape, spiral yarn shaped, foam shape, non-woven fabrics shape, screen cloth shape, felt shape or expansion shape.Wherein, preferred foil-shaped and plate shape.
By above-mentioned electrolysis tech, formed plated film to cover cathode surface as substrate.
As anode (positive pole), can use any known electrically-conductive backing plate without restriction.This anode material is preferably selected from the platinum and the graphite of plating liquid chemistry and electrochemical stability and can cause the aluminium of the plating liquid pollution that causes because of dissolving.
The form of antianode is not particularly limited.This anode can be for example plate shape and volution.
Below, will illustrate according to nano-sized carbon/aluminum composite of the present invention.
In the present invention, nano-sized carbon/aluminum composite is produced by above-mentioned nano-sized carbon/aluminum composite production method.
So nano-sized carbon/aluminum composite of producing not only can reach high conductivity and thermal conductivity, and can provide with weight reduction with thinner form and reduce size, thereby be suitable for as being used for power cable, lead-in wire, the high strength low weight composites of heat exchanger such as scatterer, condenser and vaporizer and trolley part etc.
For example, the plated film of nano-sized carbon/aluminum composite can form by above-mentioned electrolysis tech.
In the present invention, the nano-sized carbon content of nano-sized carbon/aluminum composite is preferably at 0.1-50%, more preferably in the scope of 0.1-20%.
If nano-sized carbon content is lower than 0.1%, the character that then described material can not obtain to expect does not wherein almost reflect the nano-sized carbon characteristic.If nano-sized carbon content surpasses 50%, then aluminium content is crossed low can not playing as the effect that forms agglutinating matrix between nano carbon particle, to such an extent as to nano-sized carbon-nano-sized carbon bonding may die down, causes the unexpected deterioration of the strength of materials.
Embodiment
The present invention will describe in further detail with reference to following examples.Yet should be noted that following examples only are illustrative, and are not intended to limit the present invention.
(embodiment 1)
At first, with 66.7: 33.3 molar ratio weighing AlCl
3And EMIC, and it is mixed by stirring.With the complete fusion of the mixture that obtains, and come refining by in this mixture, immersing one week of Al silk displacement or longer time.
The plating liquid that is used for the production of MWCNT/ aluminum composite prepares by add 0.1-30.0g/L multi-walled carbon nano-tubes (MWCNT with 1.2-2.0nm pipe diameter and 2-5 μ m pipe range) to said mixture.
By this plating liquid of constant current electrolysis under fully stirring, prepare the NWCNT/ aluminum composite then.
Here, the preparation of plating liquid and electrolysis are carried out under dry nitrogen atmosphere.In the constant current electrolysis, adopt to have Cu plate (99.96%) negative electrode and Al plate (99.99%) anodic dual-electrode electrolysis groove.Described negative electrode uses the 10vol%HCl acid treatment to come pre-treatment by sand paper (No.2000) grinding, with 10% sodium metasilicate aqueous electrolysis degreasing then.Electrolytic condition is set at 30 ℃ and bathes temperature, and 5,10,20,30mA/cm
2Current density and 50C/cm
2Electrolysis electricity.
The condition of surface of NWCNT/ aluminum composite is by the means monitoring of scanning electronic microscope (SEM " JSM-6500F " can be obtained by JEOL Ltd.), to observe NWCNT mixing in the al deposition thing by the mode of practicality.This observation shows that NWCNT at first is adsorbed on the deposit surface, is captured by initial Al settling nuclear (about 1-100,000 atom) then, all mixes in the Al settling nuclear of growing up, and almost completely is embedded in then in the described al deposition thing.Find that by this observation described NWCNT can form eutectic mixture (eutectic) with Al, and exists with single discrete form.
Further, MWCNT content is determined as 0.1-20% by total organic carbon amount meter (" TOC-5000A " can be obtained by SHIMADZU Corporation) in this MWCNT/ aluminum composite.
The MNCNT add-on of plating liquid and the relationship analysis between the matrix material Vickers' hardness following (referring to Fig. 1).First is made quantitatively on following supposition basis in this analysis: the increase of MWCNT eutectic mixture amount can make composite hardness increase, and the Al plated film hardness that adopts the MWCNT add-on with 0g/L as a comparative example.In the present embodiment, be set at 50,10,20 and 30mA/cm when current density
2Any one the time, Al plated film hardness is 50Hv.As shown in Figure 1, compare with the Al plated film under each current density, along with the increase of MWCNT add-on in the plating bath, the hardness of matrix material becomes higher.Based on when having nano particle in the metal, the fact that metal hardness increases usually, the eutectic mixture of MWCNT is supported by the hardness of matrix material increase among the present invention.Here, in hardness measurement, adopt Vickers' hardness survey meter (" HM-124 " can be obtained by AKASHI Co.Ltd.).
The resistivity of this matrix material is further measured by four terminal method of masurement according to JIS C 2525, and finds to be lower than the resistivity of described aluminium plated film.
Based on The above results, the nano carbon particle of other type is also analyzed.Single Walled Carbon Nanotube, carbon nanofiber, Carbon Nanohorn, soccerballene, carbon black, acetylene black and ketjen carbon black have obtained same effect by adopting arbitrarily.
Thereby obtained proof as mentioned above according to the production method of nano-sized carbon/aluminum composite of the present invention, matrix material and the validity of plating liquid.
(embodiment 2)
The EMIC and the MWCNT (having 1.2-2.0nm pipe diameter and 2-5 μ m length of tube) of predetermined amount are mixed, then by adding AlCl
3And the mixture that obtains of fusion and obtain being used for the plating liquid that the MWCNT/ aluminum composite is produced.AlCl in this plating liquid
3Be set at 66.7: 33.3 with the mol ratio of EMIC.The addition of MWCNT is set at 0.1-30.0g/L.
Then, identical with situation among the embodiment 1, under fully stirring,, produce the NWCNT/ aluminum composite by the described plating liquid of constant current electrolysis.
Here, the preparation of described plating liquid and electrolysis are carried out in dry nitrogen atmosphere.Further, described dual-electrode electrolysis groove, negative electrode pretreatment process and electrolytic condition are all identical with embodiment 1.
The condition of surface of NWCNT/ aluminum composite adopts the means of SEM to observe.Make discovery from observation, identical with the situation of embodiment 1, this NWCNT and Al form eutectic mixture and exist with single discrete form.
Further, the MWCNT content in this MWCNT/ aluminum composite is determined as 0.1-20% by total organic carbon amount meter (" TOC-5000A " can be obtained by SHIMADZU Corporation).
The MNCNT add-on of plating liquid and the relationship analysis between the matrix material Vickers' hardness following (referring to Fig. 2).Identical with the situation among the embodiment 1, this analysis adopts the Al plated film hardness with MWCNT add-on 0g/L to carry out as a comparative example based on supposition.As shown in Figure 2, compare with the Al plated film under each current density, along with the increase of MWCNT add-on in plating is bathed, the hardness of matrix material becomes higher.Based on the fact that metal hardness when having nano particle in metal raises usually, the eutectic mixture of MWCNT is supported by the hardness of matrix material increase in the present embodiment.Here, in hardness measurement, use Vickers' hardness survey meter (" HM-124 " can be obtained by AKASHI Co.Ltd.).
The resistivity of this matrix material is further measured by four terminal method of masurement, and finds that it is lower than the resistivity of Al plated film.
Based on The above results, the nano carbon particle of other type is also analyzed.Single Walled Carbon Nanotube, carbon nanofiber, Carbon Nanohorn, soccerballene, carbon black, acetylene black and ketjen carbon black have obtained same effect by adopting arbitrarily.
Thereby obtained proof as mentioned above according to the production method of nano-sized carbon/aluminum composite of the present invention, matrix material and the validity of plating liquid.
(embodiment 3)
The EMIC and the MWCNT (having 1.2-2.0nm pipe diameter and 2-5 μ m length of tube) of predetermined amount are mixed, and be added into AlCl
3-EMIC melting salt is to obtain being used for the plating liquid that the MWCNT/ aluminum composite is produced.AlCl in this plating liquid
3Be set at 66.7: 33.3 with the mol ratio of EMIC.The addition of MWCNT is set at 0.1-30.0g/L.
Then, identical with the situation of embodiment 1, under fully stirring,, produce the NWCNT/ aluminum composite by the described plating liquid of constant current electrolysis.
The preparation of plating liquid described here and electrolysis are carried out in dry nitrogen atmosphere.Further, described dual-electrode electrolysis groove, negative electrode pretreatment process and electrolytic condition are all identical with embodiment 1.
The condition of surface of NWCNT/ aluminum composite adopts the means of SEM to observe.Make discovery from observation, identical with the situation of embodiment 1, this NWCNT and Al form eutectic mixture and exist with single discrete form.
Further, the MWCNT content in this MWCNT/ aluminum composite is determined as 0.1-20% by total organic carbon amount meter (" TOC-5000A " can be obtained by SHIMADZU Corporation).
The MNCNT add-on of plating liquid and the following analysis of relation (referring to Fig. 3) between the matrix material Vickers' hardness.Identical with the situation among the embodiment 1, this analysis is carried out as a comparative example based on the Al plated film hardness that employing has MWCNT add-on 0g/L.As shown in Figure 3, compare with the Al plated film under each current density, along with the increase of MWCNT add-on in plating is bathed, the hardness of matrix material becomes higher.Based on the fact that metal hardness when having nano particle in metal raises usually, the eutectic mixture of MWCNT is supported by the hardness of matrix material increase in the present embodiment.Here, in hardness measurement, use Vickers' hardness survey meter (" HM-124 " can be obtained by AKASHI Co.Ltd.).
The resistivity of this matrix material is further measured by four terminal method of masurement, and finds that it is lower than the resistivity of Al plated film.
Based on The above results, the nano carbon particle of other type is also analyzed.Single Walled Carbon Nanotube, carbon nanofiber, Carbon Nanohorn, soccerballene, carbon black, acetylene black and ketjen carbon black have obtained same effect by adopting arbitrarily.
Thereby obtained proof as mentioned above according to the production method of nano-sized carbon/aluminum composite of the present invention, matrix material and the validity of plating liquid.
Claims (9)
1. one kind is used for the plating liquid that nano-sized carbon/aluminum composite is produced, it comprises aluminum halide, nano-sized carbon and halogenation 1,3-dialkylimidazolium and/or halogenation monoalkyl pyridine, wherein aluminum halide and halogenation 1, the mol ratio of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine is 20: 80-80: in 20 scopes; This halogenation 1, the 3-dialkylimidazolium has the alkyl of carbon number 1-12; And this halogenation monoalkyl pyridine has the alkyl of carbon number 1-12.
2. according to claim 1ly be used for the plating liquid that nano-sized carbon/aluminum composite is produced, wherein with respect to aluminum halide and halogenation 1, the amount of the cumulative volume 0.01-50g/L of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine comprises described nano-sized carbon.
3. according to claim 1ly be used for the plating liquid that nano-sized carbon/aluminum composite is produced, wherein said nano-sized carbon is to be selected from least a in the group of being made up of carbon nanotube, carbon nanofiber, Carbon Nanohorn, soccerballene, carbon black, acetylene black and ketjen carbon black.
4. the plating liquid that is used for nano-sized carbon/aluminum composite production according to claim 3, wherein said CNT (carbon nano-tube) has diameter 1-100nm, length 1-100 μ m and length-to-diameter ratio 10-100.
5. one kind is used to prepare the method that is used for the plating liquid of nano-sized carbon/aluminum composite production according to claim 1, it comprises: aluminum halide and nano-sized carbon are mixed, make the mixture and the halogenation 1 of this aluminum halide and nano-sized carbon, 3-dialkylimidazolium and/or halogenation monoalkyl pyridine mix, this aluminum halide of fusion, nano-sized carbon and halogenation 1 then, the mixture of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine; Or with nano-sized carbon and halogenation 1,3-dialkylimidazolium and/or halogenation monoalkyl pyridine mix, with this nano-sized carbon and halogenation 1, the mixture of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine mixes with aluminum halide, this aluminum halide of fusion, nano-sized carbon and halogenation 1 then, the mixture of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine.
6. one kind is used to prepare the method that is used for the plating liquid of nano-sized carbon/aluminum composite production according to claim 1, it comprises: with aluminum halide with nano-sized carbon mixes or with nano-sized carbon and halogenation 1,3-dialkylimidazolium and/or halogenation monoalkyl pyridine mix, with this nano-sized carbon mixture and aluminum halide and halogenation 1, the melting salt of 3-dialkylimidazolium and/or halogenation monoalkyl pyridine mixes then.
7. one kind by adopting the method that is used for plating liquid production nano-sized carbon/aluminum composite that nano-sized carbon/aluminum composite produces according to claim 1, and it comprises: by bathe gentle 0.01-50A/dm at 0-300 ℃ in dry oxygen-free atmosphere
2Under the electrolytic condition of current density, feed galvanic current and/or this plating liquid of pulsed current electrolysis to form plated film at substrate surface.
8. nano-sized carbon/aluminum composite of producing by nano-sized carbon according to claim 7/aluminum composite production method.
9. nano-sized carbon/aluminum composite according to claim 8, wherein the nano-sized carbon content of nano-sized carbon/aluminum composite is in the scope of 0.1-50%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005258646A JP2007070689A (en) | 2005-09-07 | 2005-09-07 | Nanocarbon/aluminum composite material, method for producing the same, and plating liquid used therefor |
| JP258646/2005 | 2005-09-07 |
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| CN101258269A true CN101258269A (en) | 2008-09-03 |
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Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20090277793A1 (en) |
| EP (1) | EP1930481A1 (en) |
| JP (1) | JP2007070689A (en) |
| CN (1) | CN101258269A (en) |
| WO (1) | WO2007029395A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102668199A (en) * | 2009-11-11 | 2012-09-12 | 日立金属株式会社 | Aluminum foil which supports carbonaceous particles scattered thereon |
| CN102041543B (en) * | 2009-10-20 | 2012-10-10 | 宝山钢铁股份有限公司 | Preparation method of fullerene/metal composite film on metal surface |
| CN104726924A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten multi-walled carbon nanotube (MWCNT) composite plating solution, plated film and preparation method thereof |
| CN107164660A (en) * | 2017-04-18 | 2017-09-15 | 中北大学 | A kind of C60Reinforced Al matrix composite and preparation method thereof |
| CN107313102A (en) * | 2017-07-03 | 2017-11-03 | 鄂尔多斯市紫荆创新研究院 | A kind of aluminium base graphene, the preparation method of CNT composite heat dissipation material |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4955268B2 (en) * | 2005-12-28 | 2012-06-20 | 東京特殊電線株式会社 | Fullerene composite plated electric wire, manufacturing method thereof, and fullerene composite plated enameled electric wire |
| KR100907804B1 (en) * | 2007-04-26 | 2009-07-16 | 주식회사 대유신소재 | Apparatus and method for aluminum plating of carbon materials using electroplating |
| GB0715258D0 (en) * | 2007-08-06 | 2007-09-12 | Univ Leuven Kath | Deposition from ionic liquids |
| KR100906746B1 (en) | 2007-12-21 | 2009-07-09 | 성균관대학교산학협력단 | Encapsulation of carbon material within aluminum |
| KR100907334B1 (en) | 2008-01-04 | 2009-07-13 | 성균관대학교산학협력단 | Method of covalent bond formation between aluminum and carbon materials, method of preparing aluminum and carbon materials composite and aluminum and carbon materials composite prepared by the same |
| DE102009035660A1 (en) * | 2009-07-30 | 2011-02-03 | Ewald Dörken Ag | Process for the electrochemical coating of a workpiece |
| WO2012091139A1 (en) | 2010-12-28 | 2012-07-05 | 独立行政法人産業技術総合研究所 | Carbon nanotube metal composite material and production method for same |
| ITRM20130146A1 (en) * | 2013-03-12 | 2014-09-13 | Stefano Guarino | ELECTROPOSITION ON METAL FOAMS |
| WO2015012275A1 (en) | 2013-07-22 | 2015-01-29 | 独立行政法人産業技術総合研究所 | Cnt metal composite material, and method for producing same |
| US20160108534A1 (en) * | 2014-10-17 | 2016-04-21 | Ut-Battelle, Llc | Aluminum deposition devices and their use in spot electroplating of aluminum |
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0445298A (en) * | 1990-06-11 | 1992-02-14 | Nisshin Steel Co Ltd | Aluminum electroplating bath |
| JP2004076031A (en) * | 2002-08-09 | 2004-03-11 | Ishikawajima Harima Heavy Ind Co Ltd | Plating bath for electroplating and plating bath for composite plating, and their production method |
| JP4032116B2 (en) * | 2002-11-01 | 2008-01-16 | 国立大学法人信州大学 | Electronic component and manufacturing method thereof |
-
2005
- 2005-09-07 JP JP2005258646A patent/JP2007070689A/en active Pending
-
2006
- 2006-06-16 WO PCT/JP2006/312152 patent/WO2007029395A1/en active Application Filing
- 2006-06-16 CN CNA2006800328310A patent/CN101258269A/en active Pending
- 2006-06-16 EP EP06766838A patent/EP1930481A1/en not_active Withdrawn
- 2006-06-16 US US12/066,027 patent/US20090277793A1/en not_active Abandoned
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041543B (en) * | 2009-10-20 | 2012-10-10 | 宝山钢铁股份有限公司 | Preparation method of fullerene/metal composite film on metal surface |
| CN102668199A (en) * | 2009-11-11 | 2012-09-12 | 日立金属株式会社 | Aluminum foil which supports carbonaceous particles scattered thereon |
| US9514887B2 (en) | 2009-11-11 | 2016-12-06 | Hitachi Metals, Ltd. | Aluminum foil with carbonaceous particles dispersed and supported therein |
| CN104726924A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten multi-walled carbon nanotube (MWCNT) composite plating solution, plated film and preparation method thereof |
| CN107164660A (en) * | 2017-04-18 | 2017-09-15 | 中北大学 | A kind of C60Reinforced Al matrix composite and preparation method thereof |
| CN107313102A (en) * | 2017-07-03 | 2017-11-03 | 鄂尔多斯市紫荆创新研究院 | A kind of aluminium base graphene, the preparation method of CNT composite heat dissipation material |
| CN107313102B (en) * | 2017-07-03 | 2019-02-26 | 鄂尔多斯市紫荆创新研究院 | A kind of preparation method of aluminium base graphene, carbon nanotube composite heat dissipation material |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007029395A1 (en) | 2007-03-15 |
| US20090277793A1 (en) | 2009-11-12 |
| JP2007070689A (en) | 2007-03-22 |
| EP1930481A1 (en) | 2008-06-11 |
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