JP2003129275A - Process for electrodepositing metal or inorganic compound using organic solvent - Google Patents
Process for electrodepositing metal or inorganic compound using organic solventInfo
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- JP2003129275A JP2003129275A JP2001319761A JP2001319761A JP2003129275A JP 2003129275 A JP2003129275 A JP 2003129275A JP 2001319761 A JP2001319761 A JP 2001319761A JP 2001319761 A JP2001319761 A JP 2001319761A JP 2003129275 A JP2003129275 A JP 2003129275A
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- Prior art keywords
- metal
- cathode
- thin film
- organic solvent
- electrolytic deposition
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電極，触媒，光触媒，
硬化膜，表面保護等の作用を呈する機能性薄膜の形成に
使用される金属又は無機化合物の電解析出方法に関す
る。The present invention relates to an electrode, a catalyst, a photocatalyst,
The present invention relates to a method for electrolytically depositing a metal or an inorganic compound, which is used for forming a functional thin film having a function of curing film, surface protection and the like.
【０００２】[0002]
【従来技術及び問題点】金属イオンを含む溶液中で電解
すると、金属イオンが電解還元されて溶液から陰極上に
析出する。電気めっきは、この現象を利用した代表的な
方法であり、Ｚｎめっき，Ｃｕめっき，Ｓｎめっき等に
従来から応用されている。また、陰極上で金属イオン以
外の化学種が電気化学的な還元反応を受けると、溶液の
ｐＨが上昇し、溶解している金属イオンが酸化物や水酸
化物として析出する。たとえば、Ｔｉ，Ｚｒ，Ｈｆ，
Ｖ，Ｎｂ，Ｔａ，Ｍｏ，Ｗ，Ｃｒ，Ａｌ等のバルブメタ
ルを含む溶液を用いた電解では、バルブメタルが酸化物
又は水酸化物となって陰極表面に析出し、耐食性の改善
に有効な保護皮膜を形成する。2. Description of the Related Art When electrolysis is carried out in a solution containing metal ions, the metal ions are electrolytically reduced and deposited from the solution on the cathode. Electroplating is a typical method utilizing this phenomenon and has been conventionally applied to Zn plating, Cu plating, Sn plating and the like. When a chemical species other than metal ions undergoes an electrochemical reduction reaction on the cathode, the pH of the solution rises and dissolved metal ions are precipitated as oxides or hydroxides. For example, Ti, Zr, Hf,
In electrolysis using a solution containing a valve metal such as V, Nb, Ta, Mo, W, Cr, or Al, the valve metal becomes an oxide or hydroxide and is deposited on the cathode surface, which is effective for improving corrosion resistance. Form a protective film.
【０００３】何れの場合も、電解析出させる金属又は金
属化合物となる金属イオンや錯イオンを含む溶液を必要
とする。そのため、イオンとなって溶液に溶解しがたい
金属種では、金属薄膜又は金属化合物薄膜の電解析出に
適用できない。また、電解析出に使用した溶液に依然と
して電解反応で消費されなかった金属イオンや錯イオン
が含まれているので、電解析出後に廃液処理が必要とな
るが、廃液処理には多大の負担がかかる。In any case, a solution containing metal ions or complex ions to be the metal or metal compound to be electrolytically deposited is required. Therefore, a metal species that is hard to be dissolved in a solution as an ion cannot be applied to electrolytic deposition of a metal thin film or a metal compound thin film. In addition, since the solution used for electrolytic deposition still contains metal ions and complex ions that have not been consumed in the electrolytic reaction, waste liquid treatment is required after electrolytic deposition, but the waste liquid treatment imposes a great burden. It takes.
【０００４】[0004]
【課題を解決するための手段】本発明は、このような問
題を解消すべく案出されたものであり、ハロゲンを添加
した有機溶媒を使用することにより、廃液処理の負担を
軽減し、金属種の溶解度による制約を受けることなく、
機能性薄膜を陰極表面に形成することを目的とする。The present invention has been devised to solve such a problem, and by using an organic solvent to which a halogen is added, the burden of waste liquid treatment can be reduced, and Without being constrained by the solubility of the species
The purpose is to form a functional thin film on the cathode surface.
【０００５】本発明の電解析出方法は、その目的を達成
するため、有機溶媒にハロゲンを添加した電解析出用溶
液を用意し、金属又は合金製の陽極及び導電性陰極を電
解析出用溶液に浸漬し、直流電解によって陽極から金属
イオンを溶出させ、金属薄膜又は金属化合物薄膜として
陰極に析出させることを特徴とする。有機溶媒には、ア
セトン，メチルエチルケトン，ジメチルケトン，ジエチ
ルケトン等のケトン類やメタノール，エタノール，プロ
パノール等のアルコール類、或いはこれらの混合物が使
用される。有機溶媒にＦ，Ｃｌ，Ｂｒ，Ｉ等のハロゲン
元素を好ましくは１０質量％以下の割合で添加すること
により、電解析出用溶液を調製する。電解析出用溶液
は、１０質量％以下の水を含むことができる。In order to achieve the object, the electrolytic deposition method of the present invention prepares a solution for electrolytic deposition in which halogen is added to an organic solvent, and uses a metal or alloy anode and a conductive cathode for electrolytic deposition. It is characterized in that it is immersed in a solution and metal ions are eluted from the anode by direct current electrolysis to deposit it on the cathode as a metal thin film or a metal compound thin film. As the organic solvent, ketones such as acetone, methyl ethyl ketone, dimethyl ketone and diethyl ketone, alcohols such as methanol, ethanol and propanol, or a mixture thereof is used. A solution for electrolytic deposition is prepared by adding halogen elements such as F, Cl, Br, and I to the organic solvent at a ratio of preferably 10 mass% or less. The electrolytic deposition solution may contain 10% by mass or less of water.
【０００６】陽極材料には種々の金属や合金を使用でき
るが、Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｍｏ，Ｗ，
Ｃｒ，Ａｌから選ばれたバルブメタル又はその合金を陽
極に使用すると、バルブメタルが金属薄膜又は酸化物や
水酸化物の皮膜となって陰極表面に堆積する。金属，セ
ラミック，ガラス，有機高分子から選ばれた１種又は２
種以上の微粒子粉体を分散させた有機溶媒を使用して直
流電解すると、金属又は金属化合物の析出と同時に微粒
子粉体が共析し、微粒子粉体が分散した複合薄膜が形成
される。この種の薄膜は、分散した微粒子粉体に応じて
種々の機能を発現する。Various metals and alloys can be used as the anode material, but Ti, Zr, Hf, V, Nb, Ta, Mo, W,
When a valve metal selected from Cr and Al or an alloy thereof is used for the anode, the valve metal becomes a metal thin film or a film of oxide or hydroxide and is deposited on the cathode surface. One or two selected from metal, ceramic, glass, organic polymer
When direct current electrolysis is performed using an organic solvent in which at least one kind of fine particle powder is dispersed, the fine particle powder is co-deposited simultaneously with the deposition of a metal or a metal compound, and a composite thin film in which the fine particle powder is dispersed is formed. This type of thin film exhibits various functions depending on the dispersed fine particle powder.
【０００７】[0007]
【作用】本発明においては、ハロゲンを添加した有機溶
媒を電解析出用溶液に使用し、陽極の金属又は合金を金
属イオンや錯イオンとして溶出させ、金属又は金属化合
物として陰極表面に析出させている。陰極表面に析出す
る金属又は金属化合物のソースを当初の電解析出用溶液
が含んでいないので、従来の電気めっきにみられるよう
な金属種の溶解度による制約を受けない。添加したハロ
ゲンは有機溶媒中でハロゲンイオンとなって存在し、一
般に電気伝導性の小さな有機溶媒を支持電解質として使
用することを可能にする。ハロゲン添加によって電気伝
導性が付与された有機溶媒中で遷移金属を陽極として電
気分解すると、通常の水性電解質を用いた電気めっきと
同様に、陽極から溶出した金属イオンが有機溶媒中を移
動して陰極表面に電解析出する。In the present invention, an organic solvent containing a halogen is used in a solution for electrolytic deposition to elute the metal or alloy of the anode as metal ions or complex ions, and deposit the metal or metal compound on the surface of the cathode. There is. Since the original solution for electrolytic deposition does not contain a source of metal or metal compound deposited on the surface of the cathode, it is not restricted by the solubility of metal species found in conventional electroplating. The added halogen is present as a halogen ion in the organic solvent and generally enables the use of an organic solvent having a small electric conductivity as a supporting electrolyte. When a transition metal is electrolyzed as an anode in an organic solvent to which electric conductivity is added by adding a halogen, the metal ions eluted from the anode move in the organic solvent as in electroplating using a normal aqueous electrolyte. Electrolytically deposits on the cathode surface.
【０００８】本発明は、バルブメタルの電解析出で従来
法と顕著に相違する。バルブメタルを陽極として有機溶
媒中で電気分解すると、有機溶媒中に各種金属イオンが
加水分解することなく安定的に存在できるため、バルブ
メタルであっても陽極溶解が容易に進行し、陰極表面に
金属バルブメタルが電解析出する。また、水分を含む有
機溶媒中でバルブメタルを電気分解すると、電気化学反
応によってバルブメタルの表面に陽極酸化皮膜が生成す
るが，ハロゲン化物イオンの腐食作用によって陽極酸化
皮膜が溶解するので，バルブメタルの酸化物が有機溶媒
中の陰極に移動した後，陰極表面に電解析出する。これ
に対し、バルブメタルを陽極として水性電解液中で陽極
分解すると、バルブメタルの表面に化学的に安定な陽極
酸化皮膜が形成され，バルブメタルは僅かに溶解するだ
けであり，陰極表面での電解析出が生じない。陽極酸化
皮膜は強酸性の水溶液中では溶解するが、このとき金属
イオンが加水分解反応を受けるので，水酸化物又は酸化
物として沈殿し，陰極表面での電解析出は依然として生
じない。The present invention is remarkably different from the conventional method in electrolytic deposition of valve metal. When electrolyzing a valve metal as an anode in an organic solvent, various metal ions can be stably present in the organic solvent without being hydrolyzed, so that even with valve metal, anodic dissolution easily progresses and Metal valve metal is electrolytically deposited. In addition, when the valve metal is electrolyzed in an organic solvent containing water, an anodic oxide film is formed on the surface of the valve metal due to an electrochemical reaction, but since the anodic oxide film is dissolved by the corrosive action of halide ions, the valve metal After moving to the cathode in the organic solvent, the oxide of 1 is electrolytically deposited on the cathode surface. On the other hand, when the valve metal is used as an anode and anodically decomposed in an aqueous electrolyte, a chemically stable anodized film is formed on the surface of the valve metal, and the valve metal is only slightly dissolved. No electrolytic deposition occurs. The anodic oxide film dissolves in a strongly acidic aqueous solution, but at this time, metal ions undergo a hydrolysis reaction, so that it precipitates as a hydroxide or oxide, and electrolytic deposition on the cathode surface does not occur yet.
【０００９】金属の種類に拘らず、電解析出が可能なこ
とも本発明の長所である。水性溶媒を用いた電解析出で
は、金属の種類に応じて溶媒の水素イオン濃度を調整す
る必要があり、溶解条件を個別に検討することを余儀な
くされる。他方、有機溶媒を用いた電解析出は、溶解度
による制約を受けることなくあらゆる種類の金属に適用
できる。また、バルブメタルの電解析出では、有機溶媒
に対する水添加の有無によって析出物の酸化状態が制御
される。たとえば、Ｔｉを電解析出するとき、無水の有
機溶媒では金属Ｔｉが陰極に析出するが、水添加によっ
て水和酸化物が陰極表面に析出する。It is also an advantage of the present invention that electrolytic deposition is possible regardless of the type of metal. In electrolytic deposition using an aqueous solvent, it is necessary to adjust the hydrogen ion concentration of the solvent according to the type of metal, and it is unavoidable to study the dissolution conditions individually. On the other hand, electrolytic deposition using organic solvents can be applied to all types of metals without being constrained by solubility. Further, in electrolytic deposition of valve metal, the oxidation state of the deposit is controlled depending on the presence or absence of water addition to the organic solvent. For example, when electrolytically depositing Ti, metallic Ti is deposited on the cathode in an anhydrous organic solvent, but hydrated oxide is deposited on the cathode surface by addition of water.
【００１０】電解析出用溶液には、電気化学的に溶解又
は酸化溶解する金属や合金が陽極として浸漬される。金
属薄膜を陰極表面に形成する場合、Ａｕ，Ａｇ，Ｃｕ，
Ｎｉ，Ｆｅ，Ｃｏ，Ｚｎ，Ｓｎ，Ｐｄ等の遷移金属又は
これらの合金が使用される。金属化合物薄膜を陰極表面
に形成する場合、Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，
Ｍｏ，Ｗ，Ｃｒ，Ａｌ等のバルブメタルが使用される。
陰極は、導電性を呈するものである限り材質に特段の制
約を受けるものではなく、金属，合金，黒鉛等を使用で
きる。メタライズ処理で導電性を付与した絶縁材料等も
陰極に使用可能である。A metal or alloy that is electrochemically dissolved or oxidized and dissolved is immersed as an anode in the electrolytic deposition solution. When a metal thin film is formed on the cathode surface, Au, Ag, Cu,
Transition metals such as Ni, Fe, Co, Zn, Sn and Pd or alloys thereof are used. When a metal compound thin film is formed on the cathode surface, Ti, Zr, Hf, V, Nb, Ta,
Valve metals such as Mo, W, Cr and Al are used.
The material of the cathode is not particularly limited as long as it exhibits conductivity, and a metal, an alloy, graphite or the like can be used. An insulating material or the like that has been made conductive by metallization can also be used for the cathode.
【００１１】ハロゲンの添加により有機溶媒に電気伝導
性が付与されるが、過剰量のハロゲンを添加すると金属
化合物薄膜に多量のハロゲンが不純物として混入する。
そのため、ハロゲン添加量を１０質量％以下に規制する
ことが好ましい。また、有機溶媒に水を含ませると、ハ
ロゲンと同様に電気伝導性が発現するが、過剰量の水分
は水の電気分解反応が主反応となるため好ましくない。
そのため、水分を添加する場合には上限を１０質量％以
下に規制することが好ましい。電解析出に際しては、１
〜１００Ｖ／ｃｍの電圧を陽極と陰極に印加し、電流密
度１ｍＡ〜１μＡ／ｃｍ2で直流電解することが好まし
い。遷移金属等の陽極溶解しやすい金属は数ボルトの電
圧印加で陰極に電解析出するが、バルブメタルでは表面
に生じている絶縁性酸化皮膜の溶解に数十〜百ボルトの
電圧を必要とする。The addition of halogen imparts electric conductivity to the organic solvent, but when an excessive amount of halogen is added, a large amount of halogen is mixed as an impurity in the metal compound thin film.
Therefore, it is preferable to regulate the amount of halogen added to 10% by mass or less. Further, when water is contained in the organic solvent, electric conductivity is developed like halogen, but an excessive amount of water is not preferable because the electrolysis reaction of water becomes a main reaction.
Therefore, when adding water, the upper limit is preferably regulated to 10% by mass or less. 1 for electrolytic deposition
It is preferable to apply a voltage of ˜100 V / cm to the anode and the cathode and to carry out direct current electrolysis at a current density of 1 mA to 1 μA / cm 2 . Metals such as transition metals that are easy to dissolve in the anode are electrolytically deposited on the cathode by applying a voltage of several volts, but valve metals require a voltage of several tens to hundreds of volts to dissolve the insulating oxide film formed on the surface. .
【００１２】微粒子粉体を有機溶媒に分散させた電解析
出用溶液を使用すると、金属や金属化合物が溶液から陰
極表面に析出する際に微粒子粉体が共析する。生成した
薄膜は、単に有機溶媒に微粒子を分散させたスラリーを
用いた電気泳動で成膜した場合に比較して密着性が良好
である。密着性の向上は、陽極溶解した金属イオンが陰
極析出する際に微粒子粉体の隙間を充填するように析出
する結果であると推察される。共析可能な微粒子粉体と
しては、遷移金属，希土類金属等の金属又は合金、各種
金属の酸化物，窒化物，炭化物，炭窒化物，複合酸化物
等のセラミック、ガラス、ポリスチレン，ポリ塩化ビニ
ル，フッ素樹脂等の有機高分子がある。たとえば、ニッ
ケル薄膜にアルミナ，チタニアを共析させると触媒活性
が付与され、炭化ケイ素を共析させると耐磨耗性が付与
された複合薄膜が得られる。電解析出に使用された廃液
は、低沸点の有機溶媒を主成分とする揮発しやすい溶液
であり、有機溶媒に残留している金属イオンの濃度も極
めて低い。そのため、従来法に比較して廃液処理にかか
る負担も大幅に軽減される。When an electrolytic deposition solution in which fine particle powder is dispersed in an organic solvent is used, fine particle powder is co-deposited when a metal or a metal compound is deposited from the solution on the cathode surface. The formed thin film has good adhesion as compared with a case where the thin film is formed by electrophoresis using a slurry in which fine particles are simply dispersed in an organic solvent. It is speculated that the improvement in the adhesion is a result of the metal ions dissolved in the anode being deposited so as to fill the gaps of the fine particle powder during the cathode deposition. Eutectoid fine particles include metals or alloys such as transition metals and rare earth metals, oxides of various metals, ceramics such as nitrides, carbides, carbonitrides and complex oxides, glass, polystyrene, polyvinyl chloride. , There are organic polymers such as fluororesins. For example, when a nickel thin film is co-deposited with alumina and titania, catalytic activity is imparted, and when silicon carbide is co-deposited, a wear-resistant composite thin film is obtained. The waste liquid used for electrolytic deposition is a solution containing an organic solvent having a low boiling point as a main component and easily volatilized, and the concentration of metal ions remaining in the organic solvent is also extremely low. Therefore, compared with the conventional method, the burden on the waste liquid treatment is significantly reduced.
【００１３】[0013]
【実施例１】アセトン２０ｍｌにヨウ素２０ｍｇを溶解
させた電解析出用溶液を用意した。１ｃｍ×１ｃｍの純
チタン板を陽極１，１ｃｍ×１ｃｍの白金基板を陰極２
として電解析出用溶液３に浸漬し（図１）、陽極１と陰
極２との電極間距離を１ｃｍに設定した。陽極１，陰極
２に５０Ｖの電圧を印加すると、陽極１／陰極２間に１
ｍＡの電流が流れ、陰極２の表面にチタン化合物が薄膜
として析出した。このときの電解反応は、次のように考
えられる。Example 1 A solution for electrolytic deposition was prepared by dissolving 20 mg of iodine in 20 ml of acetone. A 1 cm x 1 cm pure titanium plate is the anode 1, and a 1 cm x 1 cm platinum substrate is the cathode 2.
Was immersed in the electrolytic deposition solution 3 (FIG. 1), and the distance between the electrodes of the anode 1 and the cathode 2 was set to 1 cm. When a voltage of 50 V is applied to the anode 1 and the cathode 2, 1 is applied between the anode 1 and the cathode 2.
A current of mA flowed, and a titanium compound was deposited as a thin film on the surface of the cathode 2. The electrolytic reaction at this time is considered as follows.
【００１４】 [0014]
【００１５】陰極表面に堆積したチタン化合物薄膜は、
膜厚が２μｍで良好な密着性で白金基板に付着してい
た。このチタン化合物薄膜をＥＰＭＡで元素分析したと
ころ、チタン，酸素，ヨウ素，炭素が含まれていること
が判った（図２）。作製されたチタン化合物薄膜は、白
色半透明の非晶質薄膜であり、アセトアルデヒドの気相
分解反応に対して光触媒作用を呈した。アセトン２０ｍ
ｌにヨウ素２０ｍｇを添加することにより調製した電解
析出用溶液を用いてチタン化合物薄膜を形成した後、電
解析出用溶液から試験液をサンプリングし、液中の残留
チタン濃度を測定した。チタン濃度の測定には、乾燥に
よってアセトンを蒸発除去した後、残留物を塩酸に溶解
し、誘導プラズマ結合発光分析計で測定する方法を採用
した。The titanium compound thin film deposited on the cathode surface is
It had a film thickness of 2 μm and adhered to the platinum substrate with good adhesion. Elemental analysis of this titanium compound thin film by EPMA revealed that it contained titanium, oxygen, iodine, and carbon (FIG. 2). The produced titanium compound thin film was a white translucent amorphous thin film, and exhibited a photocatalytic action for the gas phase decomposition reaction of acetaldehyde. Acetone 20m
After forming a titanium compound thin film using a solution for electrolytic deposition prepared by adding 20 mg of iodine to 1, a test solution was sampled from the solution for electrolytic deposition, and the residual titanium concentration in the solution was measured. To measure the titanium concentration, a method was used in which acetone was removed by evaporation by drying, the residue was dissolved in hydrochloric acid, and measurement was performed with an inductively coupled plasma emission spectrometer.
【００１６】表１の測定結果にみられるように、電解析
出用溶液の残留チタン濃度は大幅に低い値であった。因
みに、１×１０-2Ｍ (ＮＨ4)2ＴｉＯ(Ｃ2Ｏ4)2と２.５
×１０-3Ｍ (ＣＯＯＨ)2の混合水溶液（チタン濃度：１
×１０-2Ｍ）を用いてチタン酸化物を電解析出させた場
合（Journal of Physical Chemistry B, vol.104 (200
0), p4204）、電解析出で生じるチタン化合物の量が極
めて少ないため電解析出後も混合水溶液のチタン濃度が
ほとんど変化しないものと考えられる。すなわち、残留
チタン濃度は本発明例に比較して二桁以上高く、廃液処
理に大きな負担がかかることになる。As can be seen from the measurement results in Table 1, the residual titanium concentration in the electrolytic deposition solution was significantly low. By the way, 1 × 10 -2 M (NH 4 ) 2 TiO (C 2 O 4 ) 2 and 2.5
× 10 −3 M (COOH) 2 mixed aqueous solution (Titanium concentration: 1
When titanium oxide is electrolytically deposited using (10 −2 M) (Journal of Physical Chemistry B, vol. 104 (200
0), p4204), it is considered that the titanium concentration in the mixed aqueous solution hardly changes even after electrolytic deposition because the amount of titanium compound produced by electrolytic deposition is extremely small. That is, the residual titanium concentration is two or more orders of magnitude higher than that of the examples of the present invention, and a heavy burden is imposed on waste liquid treatment.
【００１７】 [0017]
【００１８】[0018]
【実施例２】アセトン２０ｍｌ，ヨウ素２０ｍｇの溶液
に粒径０.１μｍのＳｉＯ微粒子１０ｍｇを分散させる
ことにより電解析出用溶液を調製した。電解析出用溶液
に陽極１としてSUS304ステンレス鋼板，陰極２として白
金基板を浸漬し、陽極１−陰極２に電圧５０Ｖを印加し
て直流電解した。電解析出を１０分継続した後で、電解
析出用溶液から陰極２を引き上げ、陰極表面を観察した
ところ、膜厚６μｍの薄膜が陰極表面に形成されてい
た。作製された薄膜をＥＰＭＡで元素分析した結果、Ｓ
ｉＯに相当する元素分布をもつ電着膜がＦｅリッチの界
面層を介して白金基板（陰極）に付着していることが判
った。ＳｉＯの共析は、陽極１の溶解で生じたＦｅイオ
ンが溶液中のＳｉＯ微粒子に吸着され、微粒子全体がプ
ラスに帯電されて陰極２に電気泳動したことによるもの
と推察される。作製された複合薄膜は、化学的安定性，
耐薬品性，絶縁性等に優れたＳｉＯの特性を活用し、表
面保護特性が改善された機能薄膜として使用される。Example 2 A solution for electrolytic deposition was prepared by dispersing 10 mg of SiO fine particles having a particle size of 0.1 μm in a solution of 20 ml of acetone and 20 mg of iodine. A SUS304 stainless steel plate as the anode 1 and a platinum substrate as the cathode 2 were immersed in the electrolytic deposition solution, and a voltage of 50 V was applied to the anode 1-cathode 2 for direct current electrolysis. After the electrolytic deposition was continued for 10 minutes, the cathode 2 was pulled up from the electrolytic deposition solution and the surface of the cathode was observed. As a result, a thin film having a thickness of 6 μm was formed on the surface of the cathode. As a result of elemental analysis of the prepared thin film by EPMA, S
It was found that the electrodeposition film having the element distribution corresponding to iO was attached to the platinum substrate (cathode) via the Fe-rich interface layer. It is presumed that the co-deposition of SiO was due to the fact that Fe ions generated by the dissolution of the anode 1 were adsorbed by the SiO fine particles in the solution, the whole fine particles were positively charged and electrophoresed on the cathode 2. The prepared composite thin film has chemical stability,
It is used as a functional thin film with improved surface protection characteristics by utilizing the characteristics of SiO, which has excellent chemical resistance and insulation properties.
【００１９】[0019]
【発明の効果】以上に説明したように、本発明において
は、ハロゲンを添加した有機溶媒を電解析出用溶液に使
用し、陽極側で金属又は合金を溶出させ、陰極側で金属
又は金属化合物を析出させている。この方法によると
き、金属薄膜又は金属化合物薄膜のソースを含まない電
解析出用溶液が使用されるため、金属種の溶解度に拘束
されることなく、多種の金属或いはその化合物を薄膜と
して陰極表面に析出させることが可能となる。また、電
解析出後の溶液に残留する金属イオンや錯イオンの濃度
が低いため、廃液処理が本質的に不要となり、或いは廃
液処理に要する負担も大幅に軽減される。As described above, in the present invention, a halogen-added organic solvent is used in a solution for electrolytic deposition to elute a metal or alloy on the anode side and a metal or metal compound on the cathode side. Is being deposited. When this method is used, since a solution for electrolytic deposition that does not include a source of a metal thin film or a metal compound thin film is used, various metals or their compounds are formed as thin films on the cathode surface without being restricted by the solubility of metal species. It becomes possible to deposit. In addition, since the concentration of metal ions and complex ions remaining in the solution after electrolytic deposition is low, waste liquid treatment is essentially unnecessary, or the burden required for waste liquid treatment is greatly reduced.
【図１】 実施例１で使用した電解析出装置の概略図FIG. 1 is a schematic diagram of an electrolytic deposition apparatus used in Example 1.
【図２】 実施例１で作製されたチタン化合物薄膜のＥ
ＰＭＡ分析結果を示すグラフFIG. 2E of the titanium compound thin film prepared in Example 1
Graph showing PMA analysis results
【図３】 実施例２で作製されたＳｉＯ共析薄膜のＥＰ
ＭＡ分析結果を示すグラフFIG. 3 EP of SiO eutectoid thin film prepared in Example 2
Graph showing MA analysis results
Claims (4)
用溶液を用意し、金属又は合金製の陽極及び導電性陰極
を電解析出用溶液に浸漬し、直流電解によって陽極から
金属イオンを溶出させ、金属薄膜又は金属化合物薄膜と
して陰極に析出させることを特徴とする金属又は無機化
合物の電解析出方法。1. A solution for electrolytic deposition in which halogen is added to an organic solvent is prepared, a metal or alloy anode and a conductive cathode are immersed in the solution for electrolytic deposition, and metal ions are eluted from the anode by direct current electrolysis. And a metal thin film or a metal compound thin film is deposited on the cathode as a metal thin film or a metal compound thin film.
物を有機溶媒に使用する請求項１記載の電解析出方法。2. The electrolytic deposition method according to claim 1, wherein a ketone, an alcohol, or a mixture thereof is used as an organic solvent.
ｏ，Ｗ，Ｃｒ，Ａｌから選ばれたバルブメタル又はその
合金を陽極として使用する請求項１記載の電解析出方
法。3. Ti, Zr, Hf, V, Nb, Ta, M
The electrolytic deposition method according to claim 1, wherein a valve metal selected from o, W, Cr and Al or an alloy thereof is used as the anode.
から選ばれた１種又は２種以上の微粒子粉体を有機溶媒
に分散させた電解析出用溶液を使用し、直流電解時に前
記微粒子粉体を陰極に共析させる請求項１記載の電解析
出方法。4. A solution for electrolytic deposition in which one or more kinds of fine particle powder selected from metals, ceramics, glass and organic polymers are dispersed in an organic solvent, and the fine particle powder is used during direct current electrolysis. The electrolytic deposition method according to claim 1, wherein the body is co-deposited on a cathode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013119647A (en) * | 2011-12-07 | 2013-06-17 | Jfe Steel Corp | Method for manufacturing surface-treated steel sheet |
| WO2014148227A1 (en) * | 2013-03-19 | 2014-09-25 | ソニー株式会社 | Plating film, method for manufacturing same, and plated product |
-
2001
- 2001-10-17 JP JP2001319761A patent/JP3795369B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013119647A (en) * | 2011-12-07 | 2013-06-17 | Jfe Steel Corp | Method for manufacturing surface-treated steel sheet |
| WO2014148227A1 (en) * | 2013-03-19 | 2014-09-25 | ソニー株式会社 | Plating film, method for manufacturing same, and plated product |
| JPWO2014148227A1 (en) * | 2013-03-19 | 2017-02-16 | ソニー株式会社 | Plating film, manufacturing method thereof and plated product |
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| Publication number | Publication date |
|---|---|
| JP3795369B2 (en) | 2006-07-12 |
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