JPH0353099A - Method for processing ta base material - Google Patents

Method for processing ta base material

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Publication number
JPH0353099A
JPH0353099A JP18641389A JP18641389A JPH0353099A JP H0353099 A JPH0353099 A JP H0353099A JP 18641389 A JP18641389 A JP 18641389A JP 18641389 A JP18641389 A JP 18641389A JP H0353099 A JPH0353099 A JP H0353099A
Authority
JP
Japan
Prior art keywords
base material
electrolyte
sulfonic acid
acid group
processing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP18641389A
Other languages
Japanese (ja)
Inventor
Soji Tsuchiya
土屋 宗次
Toshikuni Kojima
小島 利邦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP18641389A priority Critical patent/JPH0353099A/en
Publication of JPH0353099A publication Critical patent/JPH0353099A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To easily process a Ta base material by electrolysis by using an electrolyte contg. a sulfonic acid group and a sulfonate group. CONSTITUTION:A Ta base material of a plate, foil or film shape or other shape is processed by electrolysis in a soln. of an electrolyte contg. a sulfonic acid group and a sulfonate group. The electrolyte is preferably an arom. compd. contg. a sulfonic acid group and a sulfonate group. When the surface of the Ta base material immersed in the electrolytic soln. is properly masked with an insulating film, selective etching is enabled. The surface can be made rough by controlling conditions during electrolysis and the apparent surface area can be increased.

Description

【発明の詳細な説明】 産業上の利用分野 この発明は、Ta(タンタル)の板、箔、膜などのTa
基材を、電解を利用して加工するTa基材の加工方法に
関する。
[Detailed Description of the Invention] Industrial Field of Application This invention relates to Ta (tantalum) plates, foils, films, etc.
The present invention relates to a method for processing a Ta base material in which the base material is processed using electrolysis.

従来の技術 Taは、化学的に安定な金属に属するため、たとえば、
耐酸性を要求される化学工業用装置に利用されたり、あ
るいは、電解コンデンサの電極などに利用されたりして
いる。
Conventional technology Since Ta belongs to chemically stable metals, for example,
It is used in chemical industrial equipment that requires acid resistance, or as electrodes for electrolytic capacitors.

Ta基材の加工は、たとえば、フッ化水素酸と硝酸との
混合液、または、NaOH水溶液とH202水溶液との
混合液などのエッチング液にTa基材を浸漬し、同エッ
チング液を加熱してTa基材をエッチングすることによ
り行われる。また、コンデンサには、できるだけ大きい
表面積を有するものを用いるため、Ta基材の微粒子の
焼結体を用いている。
Processing of the Ta base material is carried out, for example, by immersing the Ta base material in an etching solution such as a mixed solution of hydrofluoric acid and nitric acid, or a mixed solution of an aqueous NaOH solution and an aqueous H202 solution, and heating the etching solution. This is done by etching the Ta base material. Furthermore, in order to use a capacitor having as large a surface area as possible, a sintered body of fine particles of a Ta base material is used.

発明が解決しようとする課題 前記のようなエッチング液を用0)でTa基材の加工を
行うと、マスキング材料が除去されやすいので、エッチ
ング除去し.たい箇所としたくない箇所との選択性が悪
いという問題がある。
Problems to be Solved by the Invention When a Ta base material is processed using the above-mentioned etching solution, the masking material is easily removed. There is a problem in that the selectivity between desired and undesired areas is poor.

他方、Ta基材の平滑な表面をエッチング加工により粗
くして表面積を大きくすることも、なかなか容易ではな
い。このため、上記のように、コンデンサには、Taの
微粒子の焼結体を利用しているのである。
On the other hand, it is not easy to increase the surface area by roughening the smooth surface of the Ta base material by etching. Therefore, as mentioned above, a sintered body of Ta fine particles is used in the capacitor.

そこで、この発明は、エッチング箇所の選択性が良く、
表面を粗くすることが容易である、Ta基材の加工方法
を提供することを目的とする。
Therefore, this invention has good selectivity of etching locations,
The object of the present invention is to provide a method for processing a Ta base material, which makes it easy to roughen the surface.

課題を解決するための手段 上記目的を達成するために、この発明にかかるTa基材
の加工方法は、Ta基材を、スルホン酸基および/また
はスルホン酸塩基を有する電解質の溶液中で電解して加
工することとしている。
Means for Solving the Problems In order to achieve the above object, the method for processing a Ta base material according to the present invention includes electrolyzing a Ta base material in a solution of an electrolyte having a sulfonic acid group and/or a sulfonic acid group. It is planned that the process will be carried out using

前記Ta基材としては、Tao板、箔、膜など固体であ
れば、その形状に特に限定はない。また、Ta基材の純
度も特に限定はなく、たとえば、通常使用されているも
のが使用されつる。
The shape of the Ta base material is not particularly limited as long as it is a solid material such as a Tao plate, foil, or film. Further, the purity of the Ta base material is not particularly limited, and for example, a commonly used Ta base material may be used.

この発明では、Ta基材を電解するために、電解質とし
て、スルホン酸基およびスルホン酸塩基のうちの少なく
とも一方の基を有する化合物(以下、「電解質入」と言
う)を用いる。スルホン酸基は、− So3}{で表さ
れる1価の基であり、スルホン酸塩基は、−SO3Xで
表される1価の基である。ここで、Xは、H+、Na+
およびK+などのアルカリ金属イオン、(NR4)+な
どの1価のカチオンである。なお、Rは、H1または、
カーボン(C)の数が1〜6のアルキル基であり、4つ
ともすべて同じでもよく、いずれか1つ以上が異なって
いてもよい。
In this invention, in order to electrolyze a Ta base material, a compound having at least one of a sulfonic acid group and a sulfonic acid group (hereinafter referred to as "electrolyte-containing") is used as an electrolyte. The sulfonic acid group is a monovalent group represented by -So3}{, and the sulfonic acid group is a monovalent group represented by -SO3X. Here, X is H+, Na+
and alkali metal ions such as K+, and monovalent cations such as (NR4)+. Note that R is H1 or
It is an alkyl group having 1 to 6 carbons (C), all four of which may be the same, or one or more of which may be different.

前記電解質入としては特に限定はないが、たとえば、ス
ルホン酸基および/またはスルホン酸塩基が付与された
芳香族化合物が使用されるのが好ましい。前記芳香族化
合物には、電気化学的に安定Aものであれば、スルホン
酸基および/またはスルホン酸塩基以外の基、たとえば
、アルキル基などが1個以上付与されていてもよい。前
記電解質入として用いられる芳香族化合物としては、た
トエハ、ベンゼンスルホン酸、アルキルベンゼンスルホ
ン酸、ナフタレンスルホン酸、アルキルナフタレンスル
ホン酸、および、これらのスルホン酸の塩からなる群の
中から選ばれた少なくとも1つが使用されるのが好まし
い。このような化合物は、電気化学的に安定であるから
である。前記芳香族化合物に付与されたアルキル基とし
ては、ベンゼン環を有する化合物の場合、カーボンの数
が18まで、ナフタレン環を有する化合物の場合、カー
ボンの数が6までが付与可能である。しかし、この発明
では、前記芳香族化合物に付与されるアルキル基の長さ
や置換数などはあまり重要ではなく、電気化学的に反応
を行ったりしないことが重要である。
The electrolyte is not particularly limited, but it is preferable to use, for example, an aromatic compound provided with a sulfonic acid group and/or a sulfonic acid group. The aromatic compound may be provided with one or more sulfonic acid groups and/or groups other than sulfonic acid groups, such as alkyl groups, as long as it is electrochemically stable. The aromatic compound used as the electrolyte may be at least one selected from the group consisting of acetic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, and salts of these sulfonic acids. Preferably one is used. This is because such compounds are electrochemically stable. As the alkyl group added to the aromatic compound, in the case of a compound having a benzene ring, up to 18 carbon atoms can be added, and in the case of a compound having a naphthalene ring, up to 6 carbon atoms can be added. However, in the present invention, the length and number of substitutions of the alkyl group imparted to the aromatic compound are not so important, and it is important that no reaction occurs electrochemically.

電解に用いる電解液の溶媒としては、電気化学的に安定
で、しかも、電解質Aが可溶な溶媒であれば特に限定は
なく、水および非水溶媒のいずれを用いてもよい。前記
非水溶媒としては、たとえば、アセトニトリル、プロピ
レンカーボネート(2−オキソー4−メチル−1,3−
ジオキソラン)、ジメチルホルムアミド、γ−プチロラ
クトンなどの非水系の有機溶媒が挙げられるが、これら
に限定されkい。前記電解液の溶媒として、水を用いて
も、非水系の有機溶媒を用いても良い。
The solvent of the electrolytic solution used for electrolysis is not particularly limited as long as it is electrochemically stable and in which electrolyte A is soluble, and either water or non-aqueous solvents may be used. Examples of the non-aqueous solvent include acetonitrile, propylene carbonate (2-oxo-4-methyl-1,3-
Examples include, but are not limited to, nonaqueous organic solvents such as dioxolane), dimethylformamide, and γ-butyrolactone. As the solvent for the electrolytic solution, water may be used or a non-aqueous organic solvent may be used.

作用 この発明では、電解質として、スルホン酸基および/ま
たはスルホン酸塩基を有するものを用いるので、Ta基
材を電解により容易K加工することが可能となった。T
a基材の電解液に浸される表面を絶縁膜で適当にマスキ
ングすることにより、選択的なエッチングも可能となる
。また、電解条件をコントロールすることにより、表面
を粗く加工できて、見かけ上の表面積を増大することが
可能となった。
Function: In the present invention, since an electrolyte having a sulfonic acid group and/or a sulfonic acid group is used, it is possible to easily perform K processing on a Ta base material by electrolysis. T
Selective etching is also possible by appropriately masking the surface of the base material that will be immersed in the electrolyte with an insulating film. Furthermore, by controlling the electrolytic conditions, it has become possible to roughen the surface and increase the apparent surface area.

実施例 以下に本発明の実施例を示す。Example Examples of the present invention are shown below.

この発明では、たとえば第1図にみるように、Ta基材
1を陽極(アノード)とし、対極には、安定な電極2を
陰極(カソード)として配し、これら両極1および2の
間に直流電源3を接続し、両極1および20間に電圧を
印加して、電解を行う。これにより、Taが電解液4中
に溶出するので、Ta基材1を所望の形状に加工したり
、粗面化したりすることができる。前記安定な電極2と
しては、たとえば、Ptなとの不溶性の電極が使用され
、また、不溶性の導体皮膜で覆われた電極であってもよ
い。図中、5は電解槽である。なお、直流電源3は、電
池である必要はなく、たとえば、交流電源と交流を直流
に変えつる回路とを有するものなどであってもよい。
In this invention, for example, as shown in FIG. 1, a Ta base material 1 is used as an anode, a stable electrode 2 is arranged as a counter electrode as a cathode, and a direct current is applied between these two electrodes 1 and 2. A power source 3 is connected and a voltage is applied between the poles 1 and 20 to perform electrolysis. As a result, Ta is eluted into the electrolytic solution 4, so that the Ta base material 1 can be processed into a desired shape or its surface can be roughened. As the stable electrode 2, an insoluble electrode such as Pt is used, or an electrode covered with an insoluble conductive film may be used. In the figure, 5 is an electrolytic cell. Note that the DC power source 3 does not need to be a battery, and may be, for example, one having an AC power source and a circuit that converts AC into DC.

Ta基材と安定な電極との間に電圧を印加すると、電流
は時間に対して、第2図に曲線Rで示すような変化をす
る。初期には、Ptのような電気化学的に非常に安定な
ものと同程度の電流が流れるが、ある時間以降になると
電流が徐々に減少する。これは、Ta基材表面に絶縁膜
が形成されていくような現象が起こっていることを示す
。さらに電圧を印加し続けると、電流は再び増加してく
る。この時、Ta基材表面を観察すると、気泡が発生し
て、Ta基材がエッチングされていくことがわかる。こ
のエッチング速度は、印加する電圧値または電流値によ
って異なり、適宜設定すればよい。電圧値または電流値
が大きいほど、エッチング速度がはやくなる。Ta基材
表面を粗くするためのエッチングも、印加する電圧値(
または電流値)と通電時間をコントロールすることによ
り容易に行える。また、前記電解質入は、従来使用して
いる電解質に比べてマスキング材料を除去しにくい。こ
のため、この発明において、Ta基材表面を所望のパタ
ーンにマスキング材料(絶縁膜)で覆うことにより、エ
ッチング箇所の選択性が高くなる。
When a voltage is applied between the Ta substrate and the stable electrode, the current changes with time as shown by curve R in FIG. Initially, a current comparable to that of an electrochemically very stable material such as Pt flows, but after a certain time, the current gradually decreases. This indicates that a phenomenon in which an insulating film is formed on the surface of the Ta base material is occurring. As the voltage continues to be applied, the current increases again. At this time, when observing the surface of the Ta base material, it can be seen that bubbles are generated and the Ta base material is etched. This etching rate varies depending on the applied voltage value or current value, and may be set as appropriate. The larger the voltage value or current value, the faster the etching rate. Etching to roughen the surface of the Ta base material also depends on the applied voltage value (
This can be easily done by controlling the current value (or current value) and the energization time. In addition, the electrolyte-containing masking material is more difficult to remove than conventionally used electrolytes. Therefore, in the present invention, by covering the surface of the Ta base material with a masking material (insulating film) in a desired pattern, the selectivity of the etching location is increased.

前記マスキング材料としては特に限定はないが、たとえ
ば、被加工部分のTa基材上にパターニング可能なフォ
トレジストなど皮膜形成可能な樹脂が使われる。
The masking material is not particularly limited, but for example, a resin capable of forming a film such as a photoresist that can be patterned on the Ta base material of the processed portion is used.

なお、この発明の方法には、Ta基材を電解研摩、電解
型彫り、電解研削などの電解加工(ECM)により加工
する場合も含まれる。たとえば、Ta基材をアノードと
し、工具をカソードとし、両極を狭いすきまで対向させ
、そのすきまに速い速度で電解液(電解質入を含むもの
)を流しながら、必要に応じて両極の少なくとも一方を
動かし、両極間に高密度電流を流すことにより電解を行
うのである。このようにして加工することにより、Ta
基材は、たとえば、カソードの工具の形状に沿った形に
加工される。
Note that the method of the present invention also includes the case where the Ta base material is processed by electrolytic machining (ECM) such as electrolytic polishing, electrolytic die engraving, and electrolytic grinding. For example, the Ta base material is used as an anode, the tool is used as a cathode, the two electrodes are opposed to each other with a narrow gap, and while an electrolyte (containing electrolyte) is flowing through the gap at a high speed, at least one of the two electrodes is connected as needed. Electrolysis is performed by moving a high-density current between the two electrodes. By processing in this way, Ta
For example, the base material is processed into a shape that follows the shape of the cathode tool.

また、この発明の方法によれば、電解のために印加する
電圧値(または電流値)と印加時間をコントロールする
ことにより、Ta基材の表面を粗くして、その表面積が
10〜60倍に増大するようにすることもできる。この
ように粗面化されたTa基材をコンデンサに用いると、
コンデンサの小型化、大容量化に有用である。
Furthermore, according to the method of the present invention, by controlling the voltage value (or current value) and application time applied for electrolysis, the surface of the Ta base material is roughened, and its surface area is increased by 10 to 60 times. It can also be made to increase. When such a roughened Ta base material is used in a capacitor,
It is useful for downsizing and increasing capacitance of capacitors.

以下に具体的な実施例を示すが、この発明は下記実施例
に限定されるものではない。
Although specific examples are shown below, the present invention is not limited to the following examples.

実施例1 電解質Aとして、p一トルエンスルホン酸のテトラエチ
ルアンモニウム塩を、溶媒としてアセトニ} IJルを
用い、0.2Mの濃度の電解液を調製した。この電解液
を電解槽に入れ、アノードとじて厚み0.1朋のTaの
箔(純度99.99%)を用い、カソードとしてTa箔
の10倍の面積を持つPt板(純度99.99%)を用
い、これらを電解液に浸漬した。
Example 1 An electrolytic solution having a concentration of 0.2M was prepared using tetraethylammonium salt of p-toluenesulfonic acid as electrolyte A and acetonyl IJ as a solvent. This electrolyte was placed in an electrolytic cell, and a 0.1 mm thick Ta foil (99.99% purity) was used as the anode, and a Pt plate (99.99% purity) with an area 10 times that of the Ta foil was used as the cathode. ), and these were immersed in an electrolytic solution.

電解液の温度を26゜Cとし、Ta箔とPt板との間に
直流電圧20Vを印加し、電流密度3mA/dで通電し
て電解を行った。電流は初期から時間とともに減少して
いき、ある時間からは増大しはじめて一定値となった。
The temperature of the electrolytic solution was set to 26° C., a DC voltage of 20 V was applied between the Ta foil and the Pt plate, and electricity was applied at a current density of 3 mA/d to perform electrolysis. The current decreased with time from the beginning, and after a certain point it started to increase and reached a constant value.

3o分間以上印加しつづけたところ、Ta箔の電解液に
浸漬した部分は完全に消失しており、電解液中に白い不
溶物が沈澱していた。
When the application was continued for 30 minutes or more, the portion of the Ta foil immersed in the electrolyte completely disappeared, and white insoluble matter was precipitated in the electrolyte.

電圧を印加してから電流値が減少していき、その後、徐
々に増えていく途中の状態で、Ta箔を取り出して、そ
の表面を観察した。その結果、Ta箔表面が凹凸にエッ
チングされていて、表面があれでいた。
After the voltage was applied, the current value decreased, and then while it was in the process of gradually increasing, the Ta foil was taken out and its surface was observed. As a result, the surface of the Ta foil was etched into irregularities, and the surface was rough.

実施例2 実施例1において、電解質Aとしてp−ドデシルベンゼ
ンスルホン酸ナトリウムを用い、溶媒として水を用いた
こと以外は、実施例1と同様にしてTaの電解を行った
ところ、Ta箔のエッチングが可能であった。
Example 2 Ta electrolysis was performed in the same manner as in Example 1, except that sodium p-dodecylbenzenesulfonate was used as electrolyte A and water was used as the solvent. was possible.

実施例3 実施例1において、電解質入としてトリイソプロビルナ
フタレンスルホン酸ナトリウムを用い、溶媒として水を
用いたこと以外は、実施例1と同様にしてTaの電解を
行ったところ、Ta箔のエノチングが可能であった。
Example 3 Ta electrolysis was carried out in the same manner as in Example 1, except that sodium triisoprobylnaphthalene sulfonate was used as the electrolyte and water was used as the solvent. was possible.

発明の効果 この発明にかかるTa基材の加工方法は、以上に述べた
ように、スルホン酸基またはスルホン酸塩基を有する電
解質を用いて電解を行うので、Ta基材が容易に加工さ
れる。
Effects of the Invention As described above, in the method for processing a Ta base material according to the present invention, electrolysis is performed using an electrolyte having a sulfonic acid group or a sulfonic acid group, so that the Ta base material can be easily processed.

【図面の簡単な説明】[Brief explanation of drawings]

第1図は、この発明にかかるTa基材の加工方法の一実
施例を表す概観図、第2図は、この発明にかかるTa基
材の加工方法を行ったときの電流の時間変化の一例を示
す特性図である。 1・・・Ta基材、2・・・安定な電極、3・・・直流
電源、4・・・電解液。
FIG. 1 is an overview diagram showing an embodiment of the method for processing a Ta base material according to the present invention, and FIG. 2 is an example of the temporal change in current when the method for processing a Ta base material according to the present invention is carried out. FIG. DESCRIPTION OF SYMBOLS 1... Ta base material, 2... Stable electrode, 3... DC power supply, 4... Electrolyte solution.

Claims (1)

【特許請求の範囲】 (1)Ta基材を、スルホン酸基および/またはスルホ
ン酸塩基を有する電解質の溶液中で電解して加工するT
a基材の加工方法。 (2)電解質が非水系の有機溶媒に溶解されている請求
項1記載のTa基材の加工方法。(3)電解質が水に溶
解されている請求項1記載のTa基材の加工方法。 (4)電解質が、スルホン酸基および/またはスルホン
酸基を有する芳香族化合物である請求項1から3までの
いずれかに記載のTa基材の加工方法。 (5)芳香族化合物が、ベンゼン、アルキルベンゼン、
ナフタレンおよびアルキルナフタレンからなる群の中か
ら選ばれた少なくとも1つである請求項4記載のTa基
材の加工方法。
[Claims] (1) T processed by electrolyzing a Ta base material in a solution of an electrolyte having a sulfonic acid group and/or a sulfonic acid group.
a Processing method of base material. (2) The method for processing a Ta base material according to claim 1, wherein the electrolyte is dissolved in a non-aqueous organic solvent. (3) The method for processing a Ta base material according to claim 1, wherein the electrolyte is dissolved in water. (4) The method for processing a Ta base material according to any one of claims 1 to 3, wherein the electrolyte is a sulfonic acid group and/or an aromatic compound having a sulfonic acid group. (5) The aromatic compound is benzene, alkylbenzene,
The method for processing a Ta base material according to claim 4, wherein the Ta base material is at least one selected from the group consisting of naphthalene and alkylnaphthalene.
JP18641389A 1989-07-19 1989-07-19 Method for processing ta base material Pending JPH0353099A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP18641389A JPH0353099A (en) 1989-07-19 1989-07-19 Method for processing ta base material

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JP18641389A JPH0353099A (en) 1989-07-19 1989-07-19 Method for processing ta base material

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0993513A4 (en) * 1997-06-30 2001-04-04 Candescent Tech Corp Impedance-assisted electrochemical technique and electrochemistry for removing material, particularly excess emitter material in electron-emitting device
NL1014727C2 (en) * 2000-03-23 2001-09-25 Univ Eindhoven Tech A method for electrolytically polishing a metal in the presence of an electrolyte composition, as well as a molded article obtained by such a method.
KR20030047276A (en) * 2001-12-10 2003-06-18 김시환 Compact Disk Case and Sheet for the same, and Method for making the same
JP2003526299A (en) * 2000-03-10 2003-09-02 ノキア コーポレイション Microphone structure
JP2006283189A (en) * 2005-03-15 2006-10-19 Komag Inc Electrochemical etching
KR100644617B1 (en) * 2004-06-16 2006-11-10 삼성전자주식회사 Apparatus and method for reproducing 7.1 channel audio
WO2007026931A1 (en) * 2005-09-02 2007-03-08 Ebara Corporation Electrochemical machining method and electrochemical machining apparatus
WO2007121999A2 (en) * 2006-04-26 2007-11-01 Supramol.Lecular Systems, S.L. Electrolytic solution for the electrochemical polishing of metal articles

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0993513A4 (en) * 1997-06-30 2001-04-04 Candescent Tech Corp Impedance-assisted electrochemical technique and electrochemistry for removing material, particularly excess emitter material in electron-emitting device
JP2003526299A (en) * 2000-03-10 2003-09-02 ノキア コーポレイション Microphone structure
NL1014727C2 (en) * 2000-03-23 2001-09-25 Univ Eindhoven Tech A method for electrolytically polishing a metal in the presence of an electrolyte composition, as well as a molded article obtained by such a method.
WO2001071068A1 (en) * 2000-03-23 2001-09-27 Technische Universiteit Eindhoven Method for the electrolytic polishing of a metal in the presence of an electrolyte composition, as well as a moulded element obtained by using such a method
KR20030047276A (en) * 2001-12-10 2003-06-18 김시환 Compact Disk Case and Sheet for the same, and Method for making the same
KR100644617B1 (en) * 2004-06-16 2006-11-10 삼성전자주식회사 Apparatus and method for reproducing 7.1 channel audio
JP2006283189A (en) * 2005-03-15 2006-10-19 Komag Inc Electrochemical etching
WO2007026931A1 (en) * 2005-09-02 2007-03-08 Ebara Corporation Electrochemical machining method and electrochemical machining apparatus
WO2007121999A2 (en) * 2006-04-26 2007-11-01 Supramol.Lecular Systems, S.L. Electrolytic solution for the electrochemical polishing of metal articles
WO2007121999A3 (en) * 2006-04-26 2009-05-22 Supramol Lecular Systems S L Electrolytic solution for the electrochemical polishing of metal articles

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