JP5704026B2 - Method for manufacturing aluminum structure - Google Patents
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- JP5704026B2 JP5704026B2 JP2011197785A JP2011197785A JP5704026B2 JP 5704026 B2 JP5704026 B2 JP 5704026B2 JP 2011197785 A JP2011197785 A JP 2011197785A JP 2011197785 A JP2011197785 A JP 2011197785A JP 5704026 B2 JP5704026 B2 JP 5704026B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 25
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims description 21
- 238000000034 method Methods 0.000 title description 32
- 150000003839 salts Chemical class 0.000 claims description 95
- 229920005989 resin Polymers 0.000 claims description 94
- 239000011347 resin Substances 0.000 claims description 92
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 74
- 229910052782 aluminium Inorganic materials 0.000 claims description 74
- 238000007747 plating Methods 0.000 claims description 39
- 239000003960 organic solvent Substances 0.000 claims description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- 230000005484 gravity Effects 0.000 claims description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000004693 imidazolium salts Chemical class 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012454 non-polar solvent Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000000725 suspension Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- -1 nickel metal hydride Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000006023 eutectic alloy Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- STCBHSHARMAIOM-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;chloride Chemical compound Cl.CN1C=CN=C1 STCBHSHARMAIOM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、アルミニウムめっきによりアルミニウム構造体を形成する方法に関し、特に低コストで製造可能なアルミニウム構造体の製造方法に関する。 The present invention relates to a method for forming an aluminum structure by aluminum plating, and particularly to a method for manufacturing an aluminum structure that can be manufactured at low cost.
三次元網目構造を有する金属多孔体は、各種フィルタ、触媒担体、電池用電極など多方面に用いられている。例えばニッケルからなるセルメット（住友電気工業（株）製：登録商標）がニッケル水素電池やニッケルカドミウム電池等の電池の電極材料として使用されている。セルメットは連通気孔を有する金属多孔体であり、金属不織布など他の多孔体に比べて気孔率が高い（９０％以上）という特徴がある。これは発泡ウレタン等の連通気孔を有する多孔体樹脂の骨格表面にニッケル層を形成した後、熱処理して発泡樹脂成形体を分解し、さらにニッケルを還元処理することで得られる。ニッケル層の形成は、発泡樹脂成形体の骨格表面にカーボン粉末等を塗布して導電化処理した後、電気めっきによってニッケルを析出させることで行われる。 Metal porous bodies having a three-dimensional network structure are used in various fields such as various filters, catalyst carriers, and battery electrodes. For example, cermet made of nickel (manufactured by Sumitomo Electric Industries, Ltd .: registered trademark) is used as an electrode material for batteries such as nickel metal hydride batteries and nickel cadmium batteries. Celmet is a metal porous body having continuous air holes, and has a feature of high porosity (90% or more) compared to other porous bodies such as a metal nonwoven fabric. This can be obtained by forming a nickel layer on the surface of the porous resin skeleton having continuous air holes such as urethane foam, then heat-treating it to decompose the foamed resin molding, and further reducing the nickel. The formation of the nickel layer is performed by depositing nickel by electroplating after applying carbon powder or the like to the surface of the skeleton of the foamed resin molded body and conducting a conductive treatment.
アルミニウムは導電性、耐腐食性、軽量などの優れた特徴がある。電池用途では例えばリチウムイオン電池の正極として、アルミニウム箔の表面にコバルト酸リチウム等の活物質を塗布したものが使用されている。正極の容量を向上するためには、アルミニウムを多孔体にして表面積を大きくし、アルミニウム内部にも活物質を充填することが考えられる。そうすると電極を厚くしても活物質を利用でき、単位面積当たりの活物質利用率が向上するからである。 Aluminum has excellent characteristics such as conductivity, corrosion resistance, and light weight. In battery applications, for example, a positive electrode of a lithium ion battery is used in which an active material such as lithium cobaltate is applied to the surface of an aluminum foil. In order to improve the capacity of the positive electrode, it is conceivable that aluminum is made porous to increase the surface area and the aluminum is filled with an active material. This is because the active material can be used even if the electrode is thickened, and the active material utilization rate per unit area is improved.
アルミニウム多孔体の製造方法として、特許文献１には、内部連通空間を有する三次元網状のプラスチック基体にアークイオンプレーティング法によりアルミニウムの蒸着処理を施して、２〜２０μｍの金属アルミニウム層を形成する方法が記載されている。また、特許文献２には、三次元網目状構造を有する発泡樹脂成形体の骨格にアルミニウムの融点以下で共晶合金を形成する金属（銅等）による皮膜を形成した後、アルミニウムペーストを塗布し、非酸化性雰囲気下で５５０℃以上７５０℃以下の温度で熱処理をすることで有機成分（発泡樹脂）の消失及びアルミニウム粉末の焼結を行い、金属多孔体を得る方法が記載されている。 As a method for producing a porous aluminum body, Patent Document 1 discloses that a metal aluminum layer having a thickness of 2 to 20 μm is formed by subjecting a three-dimensional network plastic substrate having an internal communication space to aluminum vapor deposition by an arc ion plating method. A method is described. In Patent Document 2, a film made of a metal (such as copper) that forms a eutectic alloy below the melting point of aluminum is formed on the skeleton of a foamed resin molding having a three-dimensional network structure, and then an aluminum paste is applied. In addition, a method is described in which a metal porous body is obtained by performing heat treatment at a temperature of 550 ° C. or higher and 750 ° C. or lower in a non-oxidizing atmosphere to eliminate organic components (foamed resin) and sinter aluminum powder.
一方、アルミニウムのめっきは、アルミニウムの酸素に対する親和力が大きく電位が水素より低いために水溶液系のめっき浴で電気めっきを行うことが困難である。このため、従来よりアルミニウムの電気めっきは非水溶液系のめっき浴で検討が行われている。例えば、金属の表面の酸化防止などの目的でアルミニウムをめっきする技術として、特許文献３にはオニウムハロゲン化物とアルミニウムハロゲン化物とを混合溶融した低融点組成物をめっき浴として用い、浴中の水分量を２ｗｔ％以下に維持しながら陰極にアルミニウムを析出させることを特徴とする電気アルミニウムめっき方法が開示されている。 On the other hand, aluminum plating is difficult to perform in an aqueous plating bath because aluminum has a high affinity for oxygen and a lower potential than hydrogen. For this reason, conventionally, electroplating of aluminum has been studied using a non-aqueous plating bath. For example, as a technique for plating aluminum for the purpose of preventing oxidation of the surface of a metal, Patent Document 3 uses a low melting point composition in which onium halide and aluminum halide are mixed and melted as a plating bath. An electrolytic aluminum plating method is disclosed, in which aluminum is deposited on the cathode while maintaining the amount at 2 wt% or less.
上記特許文献１の方法によれば、２〜２０μｍの厚さのアルミニウム多孔体が得られるとされているが、気相法によるため大面積での製造は困難であり、基体の厚さや気孔率によっては内部まで均一な層の形成が難しい。またアルミニウム層の形成速度が遅い、設備が高価などにより製造コストが増大するなどの問題点がある。さらに、厚膜を形成する場合には、膜に亀裂が生じたりアルミニウムの脱落が生じるおそれがある。特許文献２の方法によればアルミニウムと共晶合金を形成する層が出来てしまい、純度の高いアルミニウム層が形成できない。一方アルミニウムの電気めっき方法自体は知られているものの、金属表面へのめっきが可能であるのみで、樹脂成形体表面への電気めっき、とりわけ三次元網目構造を有する多孔質樹脂成形体の表面に電気めっきする方法は知られていなかった。 According to the method of Patent Document 1, it is said that an aluminum porous body having a thickness of 2 to 20 μm can be obtained. However, since it is based on a gas phase method, it is difficult to produce a large area, and the thickness and porosity of the substrate are difficult. In some cases, it is difficult to form a uniform layer up to the inside. In addition, there are problems such as a slow formation rate of the aluminum layer and an increase in manufacturing cost due to expensive equipment. Furthermore, when a thick film is formed, there is a possibility that the film may crack or aluminum may fall off. According to the method of Patent Document 2, a layer that forms a eutectic alloy with aluminum is formed, and a high-purity aluminum layer cannot be formed. On the other hand, although the electroplating method of aluminum itself is known, it is only possible to plate on the metal surface, and electroplating on the surface of the resin molded body, especially on the surface of the porous resin molded body having a three-dimensional network structure. The method of electroplating was not known.
本発明者らは、三次元網目構造を有する多孔質樹脂成形体であってもその表面へのアルミニウムのめっきを可能とし、厚膜を均一に形成することで純度の高いアルミニウム多孔体を形成することが可能な方法として、ポリウレタンやメラミンなどの三次元網目構造を有する樹脂成形体の表面を導電化した後、溶融塩浴中でアルミニウムをめっきするアルミニウム多孔体の製造方法に想到し、既に出願済みである。溶融塩としては塩化アルミニウムとアルカリ金属塩との混合物や塩化アルミニウムとイミダゾリウム塩との混合物、塩化アルミニウムとイミダゾリウム塩との混合物に有機溶媒を添加したもの等が例示される。 The present inventors enable plating of aluminum on the surface of a porous resin molded body having a three-dimensional network structure, and form a high-purity aluminum porous body by forming a thick film uniformly. As a possible method, after conceiving a method for producing an aluminum porous body in which the surface of a resin molded body having a three-dimensional network structure such as polyurethane and melamine is made conductive and then plated with aluminum in a molten salt bath, an application has already been filed. It is done. Examples of the molten salt include a mixture of aluminum chloride and alkali metal salt, a mixture of aluminum chloride and imidazolium salt, and a mixture of aluminum chloride and imidazolium salt to which an organic solvent is added.
しかし溶融塩浴に水分や酸素が混入すると溶融塩が劣化して電流効率が低下するため、溶融塩浴中でアルミニウムをめっきする際には、低水分量で不活性ガス雰囲気とした密閉した環境で作業する必要がある。例えばアルゴン雰囲気かつ低水分としたグローブボックス内に溶融塩浴を入れて作業をすることが考えられる。このような作業は操作性が悪く、また大面積のアルミニウム多孔体を製造する場合には製造設備が複雑となり製造コストが高くなる。これは金属表面へのアルミニウムめっき等、三次元網目構造を有する多孔質樹脂成形体以外の成形体にアルミニウムをめっきする場合でも同様である。 However, if moisture or oxygen is mixed into the molten salt bath, the molten salt deteriorates and current efficiency decreases. Therefore, when aluminum is plated in the molten salt bath, it is a sealed environment with a low moisture content and an inert gas atmosphere. Need to work in. For example, it is conceivable to work by putting a molten salt bath in a glove box having an argon atmosphere and low moisture. Such operations are poor in operability, and when a large-area aluminum porous body is manufactured, the manufacturing equipment becomes complicated and the manufacturing cost increases. This is the same even when aluminum is plated on a molded body other than a porous resin molded body having a three-dimensional network structure, such as aluminum plating on a metal surface.
そこで本発明は、アルミニウムを溶融塩浴中でめっきする工程を有するアルミニウム構造体の製造方法において、グローブボックス等の複雑な設備を必要とせず、簡便な設備で低コストで製造可能なアルミニウム構造体の製造方法を提供することを課題とする。 Therefore, the present invention provides an aluminum structure that can be manufactured at a low cost with a simple facility without requiring a complex facility such as a glove box in a method for producing an aluminum structure having a step of plating aluminum in a molten salt bath. It is an object to provide a manufacturing method.
本発明は、少なくとも表面が導電化された成形体に、アルミニウムを溶融塩浴中でめっきする工程を有するアルミニウム構造体の製造方法であって、前記溶融塩の液面に、前記溶融塩よりも比重が小さく前記溶融塩と相溶しない有機溶剤からなる液層を有することを特徴とする、アルミニウム構造体の製造方法である（請求項１）。 The present invention is a method for producing an aluminum structure having a step of plating aluminum in a molten salt bath on at least a molded body having a conductive surface, and the liquid surface of the molten salt is more than the molten salt. A method for producing an aluminum structure comprising a liquid layer comprising an organic solvent having a small specific gravity and incompatible with the molten salt (Claim 1).
溶融塩よりも比重が小さく溶融塩と相溶しない有機溶剤が溶融塩の液面に存在することで、溶融塩の液面が外気と接触することを防ぐことができ、溶融塩中に侵入する酸素や水分の量を低減することができる。そのため作業雰囲気中に水分や酸素があっても溶融塩浴への影響が少なくなるので、簡便な設備でのアルミニウムめっきが可能となる。 An organic solvent having a specific gravity smaller than that of the molten salt and incompatible with the molten salt is present on the liquid surface of the molten salt, so that the liquid surface of the molten salt can be prevented from coming into contact with the outside air and enter the molten salt. The amount of oxygen and moisture can be reduced. Therefore, even if moisture or oxygen is present in the working atmosphere, the influence on the molten salt bath is reduced, so that aluminum plating can be performed with simple equipment.
前記有機溶剤は誘電率が２．２以下の非極性溶剤であると好ましい（請求項２）。極性の高い有機溶剤は吸水性が高いので有機溶剤の液層を通して溶融塩中に水分が侵入するおそれがある。誘電率が２．２以下の非極性溶剤であれば吸水性が低く溶融塩中の水分の侵入を防ぐ効果が高くなる。 The organic solvent is preferably a nonpolar solvent having a dielectric constant of 2.2 or less (Claim 2). Since a highly polar organic solvent has high water absorption, water may enter the molten salt through the liquid layer of the organic solvent. If it is a nonpolar solvent whose dielectric constant is 2.2 or less, the water absorption is low and the effect of preventing the intrusion of moisture in the molten salt is enhanced.
前記溶融塩は、イミダゾリウム塩と塩化アルミニウムとの混合塩であると好ましい（請求項３）。イミダゾリウム塩と塩化アルミニウムとの混合塩は比較的低い温度で溶融し、また導電率が高いため溶融塩浴として好ましい。イミダゾリウム塩として、１，３位にアルキル基を持つイミダゾリウムカチオンを含む塩が好ましく用いられ、特に１−エチル−３−メチルイミダゾリウムクロライドと塩化アルミニウムとの混合塩（ＡｌＣｌ３−ＥＭＩＣ）は安定性が高く分解し難いことから最も好ましく用いられる。 The molten salt is preferably a mixed salt of an imidazolium salt and aluminum chloride. A mixed salt of an imidazolium salt and aluminum chloride is preferable as a molten salt bath because it melts at a relatively low temperature and has high conductivity. As the imidazolium salt, a salt containing an imidazolium cation having an alkyl group at the 1,3-position is preferably used. Particularly, a mixed salt of 1-ethyl-3-methylimidazolium chloride and aluminum chloride (AlCl 3 -EMIC) is used. It is most preferably used because it is highly stable and hardly decomposes.
前記成形体としては、表面が導電化された樹脂成形体や、導電性を有する金属などを使用することができる。特に三次元網目構造を有する樹脂多孔体のように複雑な骨格構造を有する樹脂成形体を用いると気孔率が高いアルミニウム構造体を得ることができ、電極用途などに好適に用いることができる（請求項４）。気孔率が高い樹脂多孔体を得ることができると共に、熱分解性に優れているウレタンまたはメラミンが樹脂多孔体の材料として好ましい（請求項５）。 As the molded body, a resin molded body whose surface is made conductive, a conductive metal, or the like can be used. In particular, when a resin molded body having a complicated skeleton structure such as a porous resin body having a three-dimensional network structure is used, an aluminum structure having a high porosity can be obtained, which can be suitably used for electrode applications (claims). Item 4). A resin porous body having a high porosity can be obtained, and urethane or melamine having excellent thermal decomposability is preferred as a material for the resin porous body.
樹脂成形体表面の導電化の手法は種々のものを選択可能である。無電解めっきや気相法によるアルミニウム、ニッケル等の金属層の形成や、導電性塗料による金属やカーボン層の形成が導電化方法として挙げられる。気相法によるアルミニウム層の形成やカーボンによる導電化を行うと、めっき後のアルミニウム構造体にアルミニウム以外の金属を混入することなくでき、金属として実質的にアルミニウムのみからなる構造体を得ることができる。 Various methods for making the surface of the resin molded body conductive can be selected. Formation of a metal layer such as aluminum or nickel by electroless plating or a vapor phase method, or formation of a metal or carbon layer by a conductive paint can be cited as a conductive method. When an aluminum layer is formed by a vapor phase method or made conductive by carbon, a metal structure other than aluminum can be mixed into the aluminum structure after plating, and a structure consisting essentially of only aluminum can be obtained. it can.
以上の工程により金属層を表面に備えた樹脂成形体を有するアルミニウム構造体が得られる。各種フィルタや触媒担体などの用途によっては、このまま樹脂と金属の複合体として使用しても良い。使用環境の制約などから樹脂が無い金属構造体として用いる場合には、前記めっきする工程の後に、さらに前記樹脂多孔体を除去する工程を有する製造方法とする（請求項６）。 The aluminum structure which has the resin molding which provided the metal layer on the surface by the above process is obtained. Depending on applications such as various filters and catalyst carriers, the resin and metal composite may be used as they are. In the case of using it as a metal structure having no resin due to restrictions on the use environment, etc., the manufacturing method further includes a step of removing the porous resin body after the plating step.
本発明によれば、グローブボックス等の複雑な設備を必要とせず、簡便な設備でアルミニウムのめっきを行うことができる。そのため、アルミニウムを溶融塩浴中でめっきする工程を有するアルミニウム構造体の製造方法を低コストで提供することができる。 According to the present invention, it is possible to perform aluminum plating with simple equipment without requiring complicated equipment such as a glove box. Therefore, the manufacturing method of the aluminum structure which has the process of plating aluminum in a molten salt bath can be provided at low cost.
以下、本発明の実施の形態をアルミニウム多孔体を製造するプロセスを代表例として適宜図を参照して説明する。以下で参照する図面で同じ番号が付されている部分は同一またはそれに相当する部分である。なお、本発明はこれに限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 Hereinafter, an embodiment of the present invention will be described with reference to the drawings as appropriate, taking a process for producing a porous aluminum body as a representative example. In the drawings to be referred to below, the same reference numerals are the same or corresponding parts. In addition, this invention is not limited to this, It is shown by the claim, and it is intended that all the changes within the meaning and range equivalent to a claim are included.
（アルミニウム構造体の製造工程）
図１はアルミニウム多孔体の製造工程の一例を説明するものであり、樹脂多孔体を芯材としてアルミニウム多孔体を形成する様子を示した断面模式図である。図１（ａ）は、基体樹脂成形体の例として、三次元網目構造を有する樹脂多孔体（発泡樹脂成形体）の表面を拡大視した拡大模式図である。樹脂多孔体１を骨格として気孔が形成されている。次に樹脂多孔体表面の導電化を行う。この工程により、図１（ｂ）に示すように樹脂多孔体１の表面には薄く導電体による導電層２が形成される。続いて溶融塩中でのアルミニウムめっきを行い、導電層が形成された樹脂多孔体の表面にアルミニウムめっき層３を形成する（図１（ｃ））。これで樹脂多孔体を基材として表面にアルミニウムめっき層３が形成されたアルミニウム多孔体が得られる。さらに樹脂多孔体の除去を行う。樹脂多孔体１を分解等して消失させることにより金属層のみが残ったアルミニウム多孔体を得ることができる（図１（ｄ））。以下各工程について順を追って説明する。
(Aluminum structure manufacturing process)
FIG. 1 illustrates an example of a manufacturing process of an aluminum porous body, and is a schematic cross-sectional view showing a state in which the aluminum porous body is formed using a resin porous body as a core material. FIG. 1A is an enlarged schematic view in which the surface of a porous resin body (foamed resin molded body) having a three-dimensional network structure is enlarged as an example of a base resin molded body. Pores are formed with the resin porous body 1 as a skeleton. Next, the surface of the resin porous body is made conductive. By this step, as shown in FIG. 1B, a thin conductive layer 2 made of a conductive material is formed on the surface of the porous resin body 1. Subsequently, aluminum plating in molten salt is performed to form an aluminum plating layer 3 on the surface of the porous resin body on which the conductive layer is formed (FIG. 1 (c)). Thus, an aluminum porous body having the aluminum plating layer 3 formed on the surface using the resin porous body as a base material is obtained. Further, the resin porous body is removed. By removing the porous resin body 1 by decomposing it or the like, an aluminum porous body in which only the metal layer remains can be obtained (FIG. 1D). Hereinafter, each step will be described in order.
（樹脂多孔体の準備）
三次元網目構造を有する樹脂多孔体を準備する。樹脂多孔体の素材は任意の樹脂を選択できる。ポリウレタン、メラミン、ポリプロピレン、ポリエチレン等の発泡樹脂成形体が素材として例示できる。連続した気孔（連通気孔）を有するものであれば任意の形状の樹脂多孔体を選択できる。樹脂多孔体の気孔率は８０％〜９８％、気孔径は５０μｍ〜５００μｍとするのが好ましい。発泡ウレタン及び発泡メラミンは気孔率が高く、また気孔の連通性があるとともに熱分解性にも優れているため樹脂多孔体として好ましく使用できる。発泡ウレタンは気孔の均一性や入手の容易さ等の点で好ましく、発泡メラミンは気孔径の小さなものが得られる点で好ましい。
(Preparation of porous resin)
A resin porous body having a three-dimensional network structure is prepared. Arbitrary resin can be selected as the material of the resin porous body. Examples of the material include foamed resin moldings such as polyurethane, melamine, polypropylene, and polyethylene. A resin porous body having an arbitrary shape can be selected as long as it has continuous pores (continuous vent holes). The porosity of the resin porous body is preferably 80% to 98%, and the pore diameter is preferably 50 μm to 500 μm. Foamed urethane and foamed melamine can be preferably used as a porous resin body because they have high porosity, have pore connectivity and are excellent in thermal decomposability. Foamed urethane is preferred in terms of pore uniformity and availability, and foamed melamine is preferred in that a product having a small pore diameter can be obtained.
樹脂多孔体には発泡体製造過程での製泡剤や未反応モノマーなどの残留物があることが多く、洗浄処理を行うことが後の工程のために好ましい。樹脂多孔体の例として、発泡ウレタンを前処理として洗浄処理したものを図２に示す。樹脂成形体が骨格として三次元的に網目を構成することで、全体として連続した気孔を構成している。発泡ウレタンの骨格はその延在方向に垂直な断面において略三角形状をなしている。ここで気孔率は、次式で定義される。
気孔率＝（１−（多孔質材の重量［ｇ］／（多孔質材の体積［ｃｍ３］×素材密度）））×１００［％］
また、気孔径は、樹脂成形体表面を顕微鏡写真等で拡大し、１インチ（２５．４ｍｍ）あたりの気孔数をセル数として計数して、平均孔径＝２５．４ｍｍ／セル数として平均的な値を求める。
The resin porous body often has residues such as foaming agents and unreacted monomers in the foam production process, and it is preferable to perform a washing treatment for the subsequent steps. FIG. 2 shows an example of the porous resin body, which is obtained by washing foamed urethane as a pretreatment. The resin molded body forms a three-dimensional network as a skeleton, thereby forming continuous pores as a whole. The urethane skeleton has a substantially triangular shape in a cross section perpendicular to the extending direction. Here, the porosity is defined by the following equation.
Porosity = (1− (weight of porous material [g] / (volume of porous material [cm 3 ] × material density))) × 100 [%]
The pore diameter is an average of the average pore diameter = 25.4 mm / cell count by enlarging the surface of the resin molded body with a micrograph and counting the number of pores per inch (25.4 mm) as the number of cells. Find the value.
（樹脂多孔体表面の導電化：カーボン塗布）
導電性塗料としてのカーボン塗料を準備する。導電性塗料としての懸濁液は、好ましくは、カーボン粒子、粘結剤、分散剤および分散媒を含む。導電性粒子の塗布を均一に行うには、懸濁液が均一な懸濁状態を維持している必要がある。このため、懸濁液は、２０℃〜４０℃に維持されていることが好ましい。その理由は、懸濁液の温度が２０℃未満になった場合、均一な懸濁状態が崩れ、樹脂多孔体の網状構造をなす骨格の表面に粘結剤のみが集中して層を形成するからである。この場合、塗布されたカーボン粒子の層は剥離し易く、強固に密着した金属めっきを形成し難い。一方、懸濁液の温度が４０℃を越えた場合は、分散剤の蒸発量が大きく、塗布処理時間の経過とともに懸濁液が濃縮されてカーボンの塗布量が変動しやすい。また、カーボン粒子の粒径は、０．０１〜５μｍで、好ましくは０．０１〜０．５μｍである。粒径が大きいと多孔質樹脂多孔体の空孔を詰まらせたり、平滑なめっきを阻害する要因となり、小さすぎると十分な導電性を確保することが難しくなる。
(Conductivity of porous resin surface: Carbon coating)
Prepare carbon paint as conductive paint. The suspension as the conductive paint preferably contains carbon particles, a binder, a dispersant and a dispersion medium. In order to uniformly apply the conductive particles, the suspension needs to maintain a uniform suspension state. For this reason, it is preferable that the suspension is maintained at 20 ° C to 40 ° C. The reason is that when the temperature of the suspension is lower than 20 ° C., the uniform suspension state is lost, and only the binder is concentrated on the surface of the skeleton forming the network structure of the porous resin body to form a layer. Because. In this case, the applied carbon particle layer is easy to peel off, and it is difficult to form a metal plating that is firmly adhered. On the other hand, when the temperature of the suspension exceeds 40 ° C., the amount of evaporation of the dispersant is large, and the suspension is concentrated as the coating treatment time elapses, and the amount of carbon applied tends to fluctuate. The particle size of the carbon particles is 0.01 to 5 μm, preferably 0.01 to 0.5 μm. When the particle size is large, it becomes a factor that clogs pores of the porous porous resin body or inhibits smooth plating, and when it is too small, it is difficult to ensure sufficient conductivity.
樹脂多孔体へのカーボン粒子の塗布は、上記懸濁液に対象となる樹脂多孔体を浸漬し、絞りと乾燥を行うことで可能である。図３は実用上の製造工程の一例として、骨格となる帯状の樹脂多孔体を導電化する処理装置の構成例を模式的に示す図である。図示の如くこの装置は、帯状樹脂１１を供給するサプライボビン１２と、導電性塗料の懸濁液１４を収容した槽１５と、槽１５の上方に配置された１対の絞りロール１７と、走行する帯状樹脂１１の側方に対向して設けられた複数の熱風ノズル１６と、処理後の帯状樹脂１１を巻き取る巻取りボビン１８とを備えている。また、帯状樹脂１１を案内するためのデフレクタロール１３が適宜配置されている。以上のように構成された装置において、帯状樹脂１１はサプライボビン１２から巻き戻され、デフレクタロール１３により案内されて、槽１５内の懸濁液１４内に浸漬される。槽１５内で懸濁液１４に浸漬された帯状樹脂１１は、上方に向きを変え、懸濁液１４の液面上方の絞りロール１７の間を走行する。このとき、絞りロール１７の間隔は、帯状樹脂１１の厚さよりも小さくなっており、帯状樹脂１１は圧縮される。従って、帯状樹脂１１に含浸された過剰な懸濁液は、絞り出されて槽１５内に戻る。 The carbon particles can be applied to the resin porous body by immersing the target resin porous body in the suspension, and performing squeezing and drying. FIG. 3 is a diagram schematically showing an example of the configuration of a processing apparatus for conducting a band-shaped resin porous body serving as a skeleton as an example of a practical manufacturing process. As shown in the figure, this apparatus includes a supply bobbin 12 for supplying a belt-shaped resin 11, a tank 15 containing a conductive paint suspension 14, a pair of squeezing rolls 17 disposed above the tank 15, A plurality of hot air nozzles 16 provided to face the side of the belt-like resin 11 to be wound, and a winding bobbin 18 that winds up the belt-like resin 11 after processing. Further, a deflector roll 13 for guiding the belt-shaped resin 11 is appropriately disposed. In the apparatus configured as described above, the belt-like resin 11 is unwound from the supply bobbin 12, guided by the deflector roll 13, and immersed in the suspension 14 in the tank 15. The strip-shaped resin 11 immersed in the suspension 14 in the tank 15 changes its direction upward and travels between the squeeze rolls 17 above the liquid level of the suspension 14. At this time, the distance between the squeezing rolls 17 is smaller than the thickness of the strip-shaped resin 11, and the strip-shaped resin 11 is compressed. Therefore, the excess suspension impregnated in the belt-shaped resin 11 is squeezed out and returned to the tank 15.
続いて、帯状樹脂１１は、再び走行方向を変える。ここで、複数のノズルから構成された熱風ノズル１６が噴射する熱風により懸濁液の分散媒等が除去され、充分に乾燥された上で帯状樹脂１１は巻取りボビン１８に巻き取られる。尚、熱風ノズル１６の噴出する熱風の温度は４０℃から８０℃の範囲であることが好ましい。以上のような装置を用いると、自動的かつ連続的に導電化処理を実施することができ、目詰まりのない網目構造を有し、且つ、均一な導電層を具備した骨格が形成されるので、次工程のアルミニウムめっきを円滑に行うことができる。なお導電化はこの方法に限らず、蒸着、スパッタ、プラズマＣＶＤ等の気相法でアルミニウムを表面に付着しても良い。 Subsequently, the strip-shaped resin 11 changes the traveling direction again. Here, the suspension dispersion medium and the like are removed by hot air jetted by the hot air nozzle 16 composed of a plurality of nozzles, and the belt-like resin 11 is wound around the winding bobbin 18 after sufficiently drying. The temperature of the hot air ejected from the hot air nozzle 16 is preferably in the range of 40 ° C to 80 ° C. When the apparatus as described above is used, the conductive treatment can be carried out automatically and continuously, and a skeleton having a network structure without clogging and having a uniform conductive layer is formed. The aluminum plating in the next process can be performed smoothly. Conduction is not limited to this method, and aluminum may be attached to the surface by a vapor phase method such as vapor deposition, sputtering, or plasma CVD.
（アルミニウム層の形成：溶融塩浴中でのめっき）
次に溶融塩中で電解めっきを行い樹脂多孔体表面にアルミニウムめっき層を形成する。図４は前述の帯状樹脂に対してアルミニウムめっき処理を連続的に行うための装置の構成を模式的に示す図である。表面が導電化された帯状樹脂２１は図の左から右に送られる。
めっき漕２８内に溶融塩２３が入っており、有機溶剤層２２が溶融塩２３の液面を覆っていることで溶融塩２３と外気との接触を防いでいる。溶融塩２３中の酸素を低減するため、溶融塩２３内に乾燥窒素等の不活性ガスをバブリングしても良い。帯状樹脂２１はデフレクタロール２９により案内されて溶融塩２３に浸漬される。漕内には一対の絞りロール２５を設けており、絞りロール２５内を通過することにより帯状樹脂２１内に浸漬した有機溶剤が絞り出される。なお有機溶剤層は溶融塩の液面全体を覆っていなくても良い。例えば入口部分での帯状樹脂２１と有機溶剤層２２との接触を防ぐために、帯状樹脂２１が溶融塩２３に入る入口部分の液面には有機溶剤層を存在させないような治具を設けても良い。この場合、入口部分の液面には乾燥窒素ガス等を流すことが好ましい。
(Formation of aluminum layer: plating in molten salt bath)
Next, electrolytic plating is performed in a molten salt to form an aluminum plating layer on the surface of the porous resin body. FIG. 4 is a diagram schematically showing a configuration of an apparatus for continuously performing the aluminum plating process on the above-described belt-shaped resin. The strip-shaped resin 21 whose surface is made conductive is sent from the left to the right in the figure.
The molten salt 23 is contained in the plating basket 28, and the organic solvent layer 22 covers the liquid surface of the molten salt 23, thereby preventing contact between the molten salt 23 and the outside air. In order to reduce oxygen in the molten salt 23, an inert gas such as dry nitrogen may be bubbled into the molten salt 23. The belt-shaped resin 21 is guided by the deflector roll 29 and immersed in the molten salt 23. A pair of squeezing rolls 25 are provided in the basket, and the organic solvent immersed in the strip-shaped resin 21 is squeezed out by passing through the squeezing roll 25. Note that the organic solvent layer may not cover the entire liquid surface of the molten salt. For example, in order to prevent contact between the strip-shaped resin 21 and the organic solvent layer 22 at the inlet portion, a jig may be provided so that the organic solvent layer does not exist on the liquid surface of the inlet portion where the strip-shaped resin 21 enters the molten salt 23. good. In this case, it is preferable to flow dry nitrogen gas or the like through the liquid surface at the inlet portion.
帯状樹脂２１はガイドロール２４に沿って溶融塩２３の中を通過する。漕外に設けた電極ロール２６から帯状樹脂２１に電流を供給し、漕内に純度９９．９９％のアルミニウム板２７を設ける。表面が導電化された帯状樹脂２１を陰極、アルミニウム板２７を陽極として溶融塩中で直流電流を印加することで樹脂多孔体全体に均一に電流が流れ、樹脂多孔体の両面に均一なめっきを形成することができる。めっきを厚く均一につけるため、このような漕を複数設けても良い。 The strip-shaped resin 21 passes through the molten salt 23 along the guide roll 24. A current is supplied to the belt-shaped resin 21 from the electrode roll 26 provided outside the cage, and an aluminum plate 27 having a purity of 99.99% is provided in the cage. By applying a direct current in the molten salt with the strip-shaped resin 21 having a conductive surface as the cathode and the aluminum plate 27 as the anode, a uniform current flows through the entire porous resin body, and uniform plating is performed on both surfaces of the porous resin body. Can be formed. A plurality of such ridges may be provided in order to apply a thick and uniform plating.
溶融塩としては、塩化アルミニウムと有機塩との混合塩（共晶塩）を使用する。比較的低温で溶融する有機溶融塩浴を使用すると、基材である樹脂多孔体を分解することなくめっきができ好ましい。有機塩としてはイミダゾリウム塩、ピリジニウム塩等が使用できる。なかでも１−エチル−３−メチルイミダゾリウムクロライド（ＥＭＩＣ）、ブチルピリジニウムクロライド（ＢＰＣ）が好ましい。また溶融塩浴に１，１０−フェナントロリンを添加すると表面が平滑となり好ましい。 As the molten salt, a mixed salt (eutectic salt) of aluminum chloride and an organic salt is used. Use of an organic molten salt bath that melts at a relatively low temperature is preferable because plating can be performed without decomposing the porous resin body as a base material. As the organic salt, imidazolium salt, pyridinium salt and the like can be used. Of these, 1-ethyl-3-methylimidazolium chloride (EMIC) and butylpyridinium chloride (BPC) are preferable. Further, it is preferable to add 1,10-phenanthroline to the molten salt bath because the surface becomes smooth.
溶融塩浴の温度は塩が溶解する範囲の温度で任意に設定可能である。溶融塩の粘度を下げるために４５℃以上１００℃以下とすることが好ましい。温度が４５℃よりも低い場合は粘度を充分に低くすることができない。また温度が１００℃よりも高い場合は有機塩が分解する可能性がある。さらに好ましい温度は５０℃以上８０℃以下である。また溶融塩の粘度を下げるため、溶融塩と相溶するキシレン等の有機溶媒を混合しても良い。 The temperature of the molten salt bath can be arbitrarily set within a range in which the salt dissolves. In order to lower the viscosity of the molten salt, the temperature is preferably set to 45 ° C. or higher and 100 ° C. or lower. When the temperature is lower than 45 ° C., the viscosity cannot be lowered sufficiently. Moreover, when temperature is higher than 100 degreeC, an organic salt may decompose | disassemble. A more preferable temperature is 50 ° C. or higher and 80 ° C. or lower. In order to lower the viscosity of the molten salt, an organic solvent such as xylene compatible with the molten salt may be mixed.
有機溶剤としては、上記溶融塩よりも比重が小さく上記溶融塩と相溶しないものを使用する。このような有機溶剤は漕内で液体状の溶融塩と混合しても溶融塩と分離し、溶融塩の上面に浮いた液層を形成する。なお有機溶剤及び溶融塩の比重は、実際にめっきする際の温度の比重で比較する。有機溶剤の比重は溶融塩の比重の９０％以下とすることが好ましい。溶融塩の比重は溶融塩の種類に依存するが、３−メチルイミダゾリウムクロライドと塩化アルミニウムとの混合塩（ＡｌＣｌ３−ＥＭＩＣ）の場合１．３８程度である。これよりも比重が低いものであれば使用可能であるが、好ましくは比重１．２４以下、さらに好ましくは比重１．０以下のものを選択する。 As the organic solvent, a solvent having a specific gravity smaller than that of the molten salt and incompatible with the molten salt is used. Such an organic solvent separates from the molten salt even when mixed with the liquid molten salt in the basket, and forms a liquid layer floating on the upper surface of the molten salt. The specific gravity of the organic solvent and the molten salt is compared with the specific gravity of the temperature at the time of actual plating. The specific gravity of the organic solvent is preferably 90% or less of the specific gravity of the molten salt. The specific gravity of the molten salt depends on the type of the molten salt, but is about 1.38 in the case of a mixed salt of 3-methylimidazolium chloride and aluminum chloride (AlCl 3 -EMIC). Any specific gravity can be used as long as the specific gravity is lower than this, but the specific gravity is preferably 1.24 or less, more preferably 1.0 or less.
有機溶剤としては、ヘキサン、ヘプタン、ノナン、流動パラフィン等の炭化水素系オイルやポリジメチルシロキサン等のシリコーンオイル等を使用することができる。溶融塩への水分の侵入を防ぐため吸水性の少ない非極性の有機溶剤が好ましい。極性の指標として誘電率を用いる。例えば極性溶剤であるエタノールの誘電率は２４、１−ブタノールの誘電率は１８である。このような溶剤は吸水率が高く好ましくない。非極性有機溶剤の中でも特に誘電率が２．２以下のものを使用することが好ましい。例えばヘキサンの誘電率は２．０であり、非極性有機溶剤として好ましく使用できる。作業性の観点からは沸点が高い有機溶剤が好ましい。沸点が低いとめっき作業中に有機溶剤が揮発するからである。したがって溶融塩の溶解温度（めっき温度）よりも沸点が高い有機溶剤が好ましい。 Examples of organic solvents that can be used include hydrocarbon oils such as hexane, heptane, nonane, liquid paraffin, and silicone oils such as polydimethylsiloxane. In order to prevent moisture from entering the molten salt, a nonpolar organic solvent with low water absorption is preferred. Dielectric constant is used as an index of polarity. For example, the dielectric constant of ethanol, which is a polar solvent, is 24, and that of 1-butanol is 18. Such a solvent has a high water absorption rate and is not preferable. Among nonpolar organic solvents, those having a dielectric constant of 2.2 or less are particularly preferred. For example, the dielectric constant of hexane is 2.0, and can be preferably used as a nonpolar organic solvent. From the viewpoint of workability, an organic solvent having a high boiling point is preferable. This is because if the boiling point is low, the organic solvent volatilizes during the plating operation. Accordingly, an organic solvent having a boiling point higher than the melting temperature of the molten salt (plating temperature) is preferable.
以上の工程により骨格の芯として樹脂多孔体を有するアルミニウム構造体（アルミニウム多孔体）が得られる。各種フィルタや触媒担体などの用途によっては、このまま樹脂と金属の複合体として使用しても良い。また使用環境の制約などから樹脂が無い金属構造体として用いる場合には樹脂を除去しても良い。樹脂の除去は、有機溶媒、溶融塩、又は超臨界水による分解（溶解）、加熱分解等任意の方法で行うことができる。アルミニウムはニッケル等と異なり、一旦酸化すると還元処理が困難であるため、たとえば電池等の電極材料として使用する場合には、アルミニウムの酸化が起こりにくい方法で樹脂を除去することが好ましい。例えば以下説明する溶融塩中での熱分解により樹脂を除去する方法が好ましく用いられる。 The aluminum structure (aluminum porous body) which has a resin porous body as a core of frame | skeleton by the above process is obtained. Depending on applications such as various filters and catalyst carriers, the resin and metal composite may be used as they are. Further, the resin may be removed when used as a metal structure having no resin due to restrictions on the use environment. Removal of the resin can be performed by any method such as decomposition (dissolution) with an organic solvent, molten salt, or supercritical water, and thermal decomposition. Since aluminum is difficult to reduce once oxidized, unlike nickel or the like, for example, when used as an electrode material for a battery or the like, it is preferable to remove the resin by a method in which oxidation of aluminum hardly occurs. For example, a method of removing the resin by thermal decomposition in a molten salt described below is preferably used.
（樹脂の除去：溶融塩中熱分解）
溶融塩中での熱分解は以下の方法で行う。表面にアルミニウムめっき層を形成した樹脂多孔体を溶融塩に浸漬し、アルミニウム層に負電位を印加しながら加熱して樹脂多孔体を分解する。溶融塩に浸漬した状態で負電位を印加すると、アルミニウムを酸化させることなく樹脂多孔体を分解することができる。加熱温度は樹脂多孔体の種類に合わせて適宜選択できるが、アルミニウムを溶融させないためにはアルミニウムの融点（６６０℃）以下の温度で処理する必要がある。好ましい温度範囲は５００℃以上６００℃以下である。また印加する負電位の量は、アルミニウムの還元電位よりマイナス側で、かつ溶融塩中のカチオンの還元電位よりプラス側とする。
(Resin removal: thermal decomposition in molten salt)
Thermal decomposition in the molten salt is performed by the following method. A porous resin body having an aluminum plating layer formed on the surface is immersed in a molten salt, and heated while applying a negative potential to the aluminum layer to decompose the porous resin body. When a negative potential is applied in a state immersed in the molten salt, the porous resin body can be decomposed without oxidizing aluminum. The heating temperature can be appropriately selected according to the type of the porous resin body. However, in order not to melt aluminum, it is necessary to treat at a temperature not higher than the melting point of aluminum (660 ° C.). A preferable temperature range is 500 ° C. or more and 600 ° C. or less. The amount of negative potential to be applied is on the minus side of the reduction potential of aluminum and on the plus side of the reduction potential of cations in the molten salt.
樹脂の熱分解に使用する溶融塩としては、アルミニウムの電極電位が卑となるようなアルカリ金属又はアルカリ土類金属のハロゲン化物の塩または硝酸塩が使用できる。具体的には塩化リチウム（ＬｉＣｌ）、塩化カリウム（ＫＣｌ）、塩化ナトリウム（ＮａＣｌ）、塩化アルミニウム（ＡｌＣｌ３）硝酸リチウム（ＬｉＮＯ３）、亜硝酸リチウム（ＬｉＮＯ２）、硝酸カリウム（ＫＮＯ３）、亜硝酸カリウム（ＫＮＯ２）、硝酸ナトリウム（ＮａＮＯ３）、及び亜硝酸ナトリウム（ＮａＮＯ２）からなる群より選択される１種以上を含むと好ましい。このような方法によって、表面の酸化層が薄く酸素量の少ないアルミニウム多孔体を得ることができる。 As the molten salt used for the thermal decomposition of the resin, an alkali metal or alkaline earth metal halide salt or nitrate which can lower the electrode potential of aluminum can be used. Specifically, lithium chloride (LiCl), potassium chloride (KCl), sodium chloride (NaCl), aluminum chloride (AlCl 3 ) lithium nitrate (LiNO 3 ), lithium nitrite (LiNO 2 ), potassium nitrate (KNO 3 ), It is preferable to include at least one selected from the group consisting of potassium nitrate (KNO 2 ), sodium nitrate (NaNO 3 ), and sodium nitrite (NaNO 2 ). By such a method, a porous aluminum body having a thin surface oxide layer and a small amount of oxygen can be obtained.
（実施例１）
アルゴン雰囲気かつ低水分（露点−３０℃以下）としたグローブボックス内で、約１００ｍｌの溶融塩浴（３３ｍｏｌ％ＥＭＩＣ−６７ｍｏｌ％ＡｌＣｌ３）を作製し、電解精製して溶融塩中の水分を除去した。溶融塩の比重は温度２８℃で１．３８であった。溶融塩浴中に銅板をセットして整流器の陰極側に接続し、対極のアルミニウム板（純度９９．９９％）を陽極側に接続した。電流密度１．５ＡＳＤの直流電流を印加して銅板表面にアルミニウムをめっきし、めっき前後の質量変化を測定することで電流効率を求めた。電流効率は９０〜１００％であり、溶融塩中に含まれる水分が少ないことを確認した。
(Example 1)
Approximately 100 ml of molten salt bath (33 mol% EMIC-67 mol% AlCl 3 ) is prepared in a glove box with an argon atmosphere and low moisture (dew point -30 ° C or less), and the water in the molten salt is removed by electrolytic purification. did. The specific gravity of the molten salt was 1.38 at a temperature of 28 ° C. A copper plate was set in the molten salt bath and connected to the cathode side of the rectifier, and a counter electrode aluminum plate (purity 99.99%) was connected to the anode side. A DC current having a current density of 1.5 ASD was applied to plate the copper plate with aluminum, and the current change was measured by measuring the mass change before and after plating. The current efficiency was 90 to 100%, and it was confirmed that the moisture contained in the molten salt was small.
上記の溶融塩が入った容器内に約２０ｍｌのヘキサンを入れて溶融塩の液面をヘキサン層で被覆した後、グローブボックスから取り出して大気中に放置した。放置後３時間、６時間、２４時間経過後、上記と同様の操作で銅板表面にアルミニウムをめっきして電流効率を求めた。いずれも電流効率は９０〜１００％であり、溶融塩中に含まれる水分が少ないことを確認した。 About 20 ml of hexane was put in the container containing the above molten salt, and the liquid surface of the molten salt was covered with a hexane layer, then taken out from the glove box and left in the atmosphere. After 3 hours, 6 hours, and 24 hours from standing, aluminum was plated on the surface of the copper plate in the same manner as described above to obtain current efficiency. In any case, the current efficiency was 90 to 100%, and it was confirmed that the moisture contained in the molten salt was small.
（実施例２）
上記の溶融塩が入った容器内に約２０ｍｌの流動パラフィンを入れたこと以外は実施例１と同様の操作を行い、大気中放置後３時間、６時間、２４時間電流効率を求めた。いずれも電流効率は９０〜１００％であり、溶融塩中に含まれる水分が少ないことを確認した。
(Example 2)
The same operation as in Example 1 was carried out except that about 20 ml of liquid paraffin was placed in the container containing the above molten salt, and the current efficiency was determined for 3 hours, 6 hours and 24 hours after standing in the atmosphere. In any case, the current efficiency was 90 to 100%, and it was confirmed that the moisture contained in the molten salt was small.
（比較例）
溶融塩が入った容器内にヘキサンを入れなかったこと以外は実施例１と同様の操作を行い、大気中放置後３時間での電流効率を求めた。目視でも銅板表面へのアルミニウムの付着が観察されず、銅板の質量変化もほとんどなかった。有機溶剤層を溶融塩の液面に設けない場合は溶融塩中に水分が混入して溶融塩が劣化したと思われる。
(Comparative example)
The same operation as in Example 1 was carried out except that hexane was not placed in the container containing the molten salt, and the current efficiency at 3 hours after being left in the atmosphere was determined. Even when visually observed, adhesion of aluminum to the surface of the copper plate was not observed, and there was almost no change in the mass of the copper plate. In the case where the organic solvent layer is not provided on the surface of the molten salt, it is considered that the molten salt has deteriorated due to moisture mixed in the molten salt.
１ 樹脂多孔体 ２ 導電層 ３ アルミニウムめっき層
１１ 帯状樹脂 １２ サプライボビン １３ デフレクタロール １４ 懸濁液
１５ 槽 １６ 熱風ノズル １７ 絞りロール １８ 巻取りボビン
２１ 帯状樹脂 ２２ 有機溶剤層 ２３ 溶融塩 ２４ ガイドロール
２５ 絞りロール ２６ 電極ロール ２７ アルミニウム板 ２８ 漕
２９ デフレクタロール
DESCRIPTION OF SYMBOLS 1 Resin porous body 2 Conductive layer 3 Aluminum plating layer 11 Band-shaped resin 12 Supply bobbin 13 Deflector roll 14 Suspension 15 Tank 16 Hot air nozzle 17 Drawing roll 18 Winding bobbin 21 Band-shaped resin 22 Organic solvent layer 23 Molten salt 24 Guide roll 25 Drawing roll 26 Electrode roll 27 Aluminum plate 28 漕 29 Deflector roll
Claims (6)
前記溶融塩の液面に、前記溶融塩よりも比重が小さく前記溶融塩と相溶しない有機溶剤からなる液層を有することを特徴とする、アルミニウム構造体の製造方法。 A method for producing an aluminum structure comprising a step of plating aluminum in a molten salt bath on a molded body having at least a surface made conductive,
A method for producing an aluminum structure, comprising a liquid layer made of an organic solvent having a specific gravity smaller than that of the molten salt and incompatible with the molten salt on a liquid surface of the molten salt.
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| DE2901586A1 (en) * | 1979-01-17 | 1980-07-31 | Montblanc Simplo Gmbh | ALUMINUM CELL |
| US20040173468A1 (en) * | 2003-03-05 | 2004-09-09 | Global Ionix | Electrodeposition of aluminum and refractory metals from non-aromatic organic solvents |
| JP5598027B2 (en) * | 2009-03-05 | 2014-10-01 | 日立金属株式会社 | Aluminum porous material and method for producing the same, and electricity storage device using aluminum porous material as electrode current collector |
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2011
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