JP3130056B2 - Aluminum foil for electrolytic capacitor electrodes - Google Patents
Aluminum foil for electrolytic capacitor electrodesInfo
- Publication number
- JP3130056B2 JP3130056B2 JP02401401A JP40140190A JP3130056B2 JP 3130056 B2 JP3130056 B2 JP 3130056B2 JP 02401401 A JP02401401 A JP 02401401A JP 40140190 A JP40140190 A JP 40140190A JP 3130056 B2 JP3130056 B2 JP 3130056B2
- Authority
- JP
- Japan
- Prior art keywords
- foil
- aluminum
- elements
- aluminum foil
- interface
- 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.)
- Expired - Fee Related
Links
- 239000011888 foil Substances 0.000 title claims description 71
- 229910052782 aluminium Inorganic materials 0.000 title claims description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 38
- 239000003990 capacitor Substances 0.000 title claims description 12
- 239000000758 substrate Substances 0.000 claims description 18
- 229910052738 indium Inorganic materials 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052790 beryllium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 229910001122 Mischmetal Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- -1 Z When using r Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
- F05C2203/00—Non-metallic inorganic materials
- F05C2203/04—Phosphor
Landscapes
- Physical Vapour Deposition (AREA)
- ing And Chemical Polishing (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、電解コンデンサ電極
用アルミニウム箔、特に中高圧用の陽極材料として用い
られるアルミニウム箔に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum foil for an electrolytic capacitor electrode, and more particularly to an aluminum foil used as an anode material for medium and high pressures.
【０００２】[0002]
【従来の技術】電解コンデンサ電極用アルミニウム箔
は、その実効表面積を拡大して単位面積あたりの静電容
量を増大するため、一般に電気的あるいは電気化学的な
エッチング処理により箔表面に形成されるエッチングピ
ットの密度を増大することについて、従来から多くの研
究がなされてきた。なかでも、エッチングピットの密度
は、アルミニウム箔の表面部の組成、組織に大きく影響
されることの知見から、特公昭６２−４２３７０号公報
に見られるように、表層部に、Ｐｂ、Ｂｉ、Ｉｎの群か
ら選ばれた１種以上の元素を高密度に含有せしめるもの
とする技術の有用性が提案されている。そしてかかるア
ルミニウム箔の表面にＰｂ、ＩｎおよびＢｉの少なくと
も１種以上を化合物の状態で付与し、これら金属の融点
以上の温度で熱拡散処理し、必要ならば常法に従って焼
鈍を行うものとすることが提案されている。2. Description of the Related Art An aluminum foil for an electrode of an electrolytic capacitor is generally formed on the foil surface by an electrical or electrochemical etching process in order to increase the effective surface area and increase the capacitance per unit area. Much research has been done on increasing the density of pits. Above all, from the knowledge that the density of etching pits is greatly affected by the composition and structure of the surface portion of the aluminum foil, as seen in JP-B-62-42370, Pb, Bi, In The usefulness of a technique for allowing one or more elements selected from the group to be contained at a high density has been proposed. Then, at least one of Pb, In and Bi is applied in the form of a compound to the surface of the aluminum foil, subjected to a thermal diffusion treatment at a temperature equal to or higher than the melting point of these metals, and if necessary, annealed according to a conventional method. It has been proposed.
【０００３】[0003]
【発明が解決しようとする課題】この発明は、上記のよ
うな従来技術の背景の中で、アルミニウム箔の表面に高
濃度に含有せしめて拡面率の増大に寄与せしめ得る元素
を探索すると共に、最も拡面率の拡大に有効な分布状態
と分布量との関係を見出だすことにより、静電容量の増
大を図り得る電解コンデンサ電極用アルミニウム箔を提
供することを目的とする。SUMMARY OF THE INVENTION In the background of the prior art as described above, the present invention seeks for an element which can be contained in a high concentration on the surface of an aluminum foil to contribute to an increase in the area coverage. It is another object of the present invention to provide an aluminum foil for an electrolytic capacitor electrode capable of increasing the capacitance by finding a relationship between a distribution state and a distribution amount which is most effective for increasing the surface area.
【０００４】[0004]
【課題を解決するための手段】この発明は、上記拡面率
の増大に有効に寄与するエッチング核生成元素を選択
し、これを箔の所定部位に特定の濃度範囲に濃化状態に
含有せしめるようにしたものである。According to the present invention, an etching nucleation element which effectively contributes to the increase in the surface area is selected and is contained in a predetermined region of the foil in a specific concentration range in a concentrated state. It is like that.
【０００５】而して、この発明は、アルミニウム純度が
９９．９％以上でかつＣｕ、Ｓｉ、Ｚｎ、Ｍｎ、Ｇａ、
Ｐ、Ｖ、Ｔｉ、Ｃｒ、Ｎｉ、Ｔａ、Ｚｒ、Ｃ、Ｂｅ、Ｐ
ｂ、Ｉｎ、希土類元素のうち１種または２種以上の元素
を含有するアルミニウム箔からなり、上記元素が箔基体
とその表面に形成された酸化皮膜との界面部に濃化状態
に含有されると共に、該界面部における上記元素の濃度
が箔基体内層部に対するイオン強度比で１．２〜３０の
範囲に設定されてなることを特徴とする電解コンデンサ
電極用アルミニウム箔を要旨とする。[0005] Thus, the present invention provides an aluminum alloy having an aluminum purity of 99.9% or more and Cu, Si, Zn, Mn, Ga,
P, V, Ti, Cr, Ni, Ta, Zr, C, Be, P
b, In, an aluminum foil containing one or more of the rare earth elements, and the above elements are contained in a concentrated state at the interface between the foil substrate and the oxide film formed on the surface thereof. In addition, an aluminum foil for an electrode of an electrolytic capacitor is characterized in that the concentration of the element at the interface is set in a range of 1.2 to 30 as an ion intensity ratio with respect to the inner layer of the foil substrate.
【０００６】この発明において、アルミニウム箔の全体
としてのアルミニウム純度に９９．９％以上を必要とさ
れるのは、上記未満の純度では電解エッチング時にエッ
チングピットの成長が多くの不純物の存在によって阻害
され、均一な深いトンネル状ピットを形成できず、従っ
て静電容量の高いアルミニウム箔を得ることができない
ためである。好ましくはアルミニウム純度９９．９８％
以上のものを用いるのが良い。In the present invention, the reason why the aluminum purity of the entire aluminum foil is required to be 99.9% or more is that if the purity is less than the above, the growth of etching pits during electrolytic etching is hindered by the presence of many impurities. This is because a uniform deep tunnel-like pit cannot be formed, and thus an aluminum foil having a high capacitance cannot be obtained. Preferably aluminum purity 99.98%
It is better to use the above.
【０００７】アルミニウム箔の箔基体とその表面に形成
された酸化皮膜との界面部に、図１に示すように、エッ
チング核形成元素の１種以上を高濃度に含有せしめるも
のとすることは、静電容量の増大効果を得るための主要
素をなすものである。この効果が得られる理由は、酸化
皮膜と箔基体との界面部に濃化した元素がエッチング核
として作用し、多数のエッチングピットが形成され、以
後箔内部にトンネル状に深く進行するため、より大きな
拡面率が得られることによるものと考えられる。 上記
界面部における上記元素の濃度は、箔基体内層部に対す
るイオン強度比で１．２〜３０の範囲に含有されている
ことが必要である。下限値未満では、エッチングピット
の密度が不十分なものとなり、拡面率の増大が期待でき
ないからであり、一方、上限値を超えると、アルミニウ
ム箔表面の耐食性が著しく低下してエッチングピットが
限度を超えて高密度に形成される結果ピット同志が合体
して実質的な箔表面の全面溶解につながり、かえって表
面積が小さいものとなる。最も好ましいイオン強度比の
範囲は、概ね３〜２５である。[0007] As shown in FIG. 1, it is required that one or more kinds of etching nucleation elements are contained in a high concentration at an interface between an aluminum foil foil substrate and an oxide film formed on the surface thereof. This is the main element for obtaining the effect of increasing the capacitance. The reason that this effect is obtained is that the element concentrated at the interface between the oxide film and the foil substrate acts as an etching nucleus, and a large number of etching pits are formed. This is considered to be due to the fact that a large area enlargement ratio was obtained. It is necessary that the concentration of the element at the interface is in the range of 1.2 to 30 in terms of ionic strength ratio to the inner layer of the foil substrate. If the amount is less than the lower limit, the density of the etching pits becomes insufficient and an increase in the area coverage cannot be expected. On the other hand, if the amount exceeds the upper limit, the corrosion resistance of the aluminum foil surface is significantly reduced and the etching pits are limited. As a result, the pits are united with each other to substantially dissolve the entire foil surface, resulting in a smaller surface area. The most preferable range of the ionic strength ratio is approximately 3 to 25.
【０００８】ここにエッチング核形成元素としては、Ｃ
ｕ、Ｓｉ、Ｚｎ、Ｍｎ、Ｇａ、Ｐ、Ｖ、Ｔｉ、Ｃｒ、Ｎ
ｉ、Ｔａ、Ｚｒ、Ｃ、Ｂｅ、Ｐｂ、Ｉｎ、希土類元素が
用いられる。なお、希土類元素は原子番号５７から７１
までの１５元素、即ちＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、
Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｉｍ、Ｙ
ｂ、ＬｕおよびこれらにＹ、Ｓｃを加えた１７元素の群
からなるものである。上述の元素はこの発明において、
アルミニウム箔のエッチングによる表面積の拡大効果に
有効に寄与するものである点で相互に均等物として評価
し得るものである。またこれらの元素は、ここに単独の
元素として用いる必要はなく、２種以上の併用が許容さ
れる。希土類元素の場合には、その混合塩化物を電解し
て得られるミッシュメタル（Ｍ・Ｍ）を用いても良く、
また入手のし易さから工業的にはＹ、Ｌａ、Ｃｅ、Ｐ
ｒ、Ｎｄ、Ｓｍ、ミッシュメタルの群から選ばれた１種
または２種以上の組み合わせにおいて用いるのが好適で
ある。Here, the etching nucleus forming element is C
u, Si, Zn, Mn, Ga, P, V, Ti, Cr, N
i, Ta, Zr, C, Be, Pb, In, and rare earth elements are used. The rare earth elements have atomic numbers 57 to 71.
15 elements, ie, La, Ce, Pr, Nd, Pm,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Im, Y
b, Lu and a group of 17 elements obtained by adding Y and Sc to them. In the present invention, the above-mentioned elements are
They can be mutually evaluated as equivalents in that they effectively contribute to the effect of increasing the surface area by etching the aluminum foil. These elements do not need to be used as single elements here, and two or more of them can be used in combination. In the case of a rare earth element, a misch metal (MM) obtained by electrolyzing a mixed chloride thereof may be used.
Industrially, Y, La, Ce, P
It is preferable to use one or a combination of two or more selected from the group consisting of r, Nd, Sm, and misch metal.
【０００９】エッチング核形成元素として、Ｃｕ、Ｓ
ｉ、Ｚｎ、Ｍｎ、Ｇａを採用する場合には、箔表面から
厚さ０．１μｍまでの箔表層部を除いた箔内部における
上記元素の濃度を３〜６０ｐｐｍの範囲に設定すること
が望ましい。またＰ、Ｖ、Ｔｉ、Ｃｒ、Ｎｉ、Ｔａ、Ｚ
ｒ、Ｃ、Ｂｅ、Ｂ、Ｍｇを採用する場合には同濃度を１
〜４０ｐｐｍの範囲、Ｐｂ、Ｉｎ、Ｂｉ、希土類元素を
採用する場合には同濃度を０．０１〜３ｐｐｍの範囲に
それぞれ設定することが望ましい。いずれの場合にも下
限値未満であるとエッチング核の形成が不十分であり、
また上限値を超えて過多に含有されても過剰エッチング
となるからである。Cu, S as etching nucleation elements
When i, Zn, Mn, and Ga are used, it is desirable to set the concentration of the above elements in the foil inside the foil except for the surface layer of the foil up to 0.1 μm in thickness from the foil surface to a range of 3 to 60 ppm. P, V, Ti, Cr, Ni, Ta, Z
When using r, C, Be, B, and Mg, the same concentration is set to 1
When Pb, In, Bi, or a rare earth element is used, the concentration is preferably set to a range of 0.01 to 3 ppm. In any case, if less than the lower limit, the formation of etching nuclei is insufficient,
In addition, excessive etching exceeding the upper limit results in excessive etching.
【００１０】Ｃｕ、Ｓｉ、Ｚｎ、Ｍｎ、Ｇａを採用した
場合におけるその好適な濃度範囲は概ね１０〜３０ｐｐ
ｍ、Ｐ、Ｖ、Ｔｉ、Ｃｒ、Ｎｉ、Ｔａ、Ｚｒ、Ｃ、Ｂ
ｅ、Ｂを採用した場合におけるその好適な濃度範囲は概
ね５〜２５ｐｐｍ、Ｐｂ、Ｉｎ、希土類元素を採用した
場合におけるその好適な濃度範囲は概ね０．２〜１．５
ｐｐｍである。When Cu, Si, Zn, Mn, and Ga are used, the preferred concentration range is generally 10 to 30 pp.
m, P, V, Ti, Cr, Ni, Ta, Zr, C, B
The preferred concentration range when e and B are adopted is about 5 to 25 ppm, and the preferred concentration range when Pb, In and rare earth elements are adopted is about 0.2 to 1.5.
ppm.
【００１１】上記した如き分布状態にエッチング核形成
元素を高濃度に含有するアルミニウム箔を製造するに
は、アルミニウム地金を溶解する段階で所要量の上記元
素の１種または２種以上を添加して鋳造した後、常法に
従って熱間圧延、箔圧延、要すればその間に更に中間焼
鈍を行って製箔し、その後これを例えば真空中において
４５０〜５５０℃で１〜３０時間、好ましくは４７０〜
５２０℃で３〜１０時間の最終焼鈍処理を施す。然る
後、箔基体とその表面の酸化皮膜の界面部に、例えばイ
オン注入により上記元素を注入することにより製造する
ことができる。地金中に添加した元素およびイオン注入
した元素は箔基体とその表面の酸化皮膜との界面部に高
濃度に拡散され、この発明の規定範囲に集中的に含有せ
しめることができる。In order to produce an aluminum foil containing the etching nucleation element at a high concentration in the above-mentioned distribution state, a required amount of one or more of the above elements is added at the stage of dissolving the aluminum base metal. After the casting, hot rolling and foil rolling are performed according to a conventional method, and if necessary, further intermediate annealing is performed to produce a foil. Thereafter, the foil is formed at 450 to 550 ° C. for 1 to 30 hours in a vacuum, preferably 470 hours. ~
A final annealing treatment is performed at 520 ° C. for 3 to 10 hours. Thereafter, it can be manufactured by injecting the above-described element into the interface between the foil substrate and the oxide film on the surface thereof, for example, by ion implantation. The element added to the base metal and the ion-implanted element are diffused at a high concentration at the interface between the foil substrate and the oxide film on the surface thereof, and can be intensively contained in the specified range of the present invention.
【００１２】[0012]
【発明の効果】この発明にかかる電解コンデンサの電極
用アルミニウム箔は、エッチング性に優れ、エッチング
処理により極めて大きな拡面率を得ることができる。特
にエッチング前処理を行うエッチング条件下においてそ
の効果が大であると共に、該エッチング時において箔表
面の全面溶解を抑制しうる。The aluminum foil for an electrode of an electrolytic capacitor according to the present invention is excellent in etching properties and can obtain an extremely large surface area by etching. In particular, the effect is great under the etching conditions for performing the pre-etching treatment, and the entire surface of the foil surface can be suppressed from being dissolved during the etching.
【００１３】従って、大きな静電容量を有し、電気的特
性に優れると共に、強度的にも優れたものとなし得る。Therefore, it has a large capacitance, excellent electrical characteristics, and excellent strength.
【００１４】[0014]
【実施例】純度９９．９９％の純アルミニウム地金（Ｓ
ｉ：０．００２％、Ｆｅ：０．００２％）にＣｕ、Ｓ
ｉ、Ｚｎ、Ｍｎ、Ｇａ、Ｐ、Ｖ、Ｔｉ、Ｃｒ、Ｎｉ、Ｔ
ａ、Ｚｒ、Ｃ、Ｂｅ、Ｐｂ、Ｉｎ、希土類元素のうちか
ら選ばれたそのうちの１種または２種以上を第１表およ
び第２表に示す各種の含有量となるように添加し、溶解
鋳造後、熱間圧延、中間焼鈍、箔圧延、洗浄、真空下で
４９０℃×４時間の焼鈍処理を施して厚さ０．１mmのア
ルミニウム箔に製造した。然る後、上記元素をイオン注
入により所定量付与して電解コンデンサ電極材としての
各種供試料を得た。EXAMPLE A pure aluminum ingot of 99.99% purity (S
i: 0.002%, Fe: 0.002%) and Cu, S
i, Zn, Mn, Ga, P, V, Ti, Cr, Ni, T
a, Zr, C, Be, Pb, In, and one or more selected from rare earth elements are added so as to have various contents shown in Tables 1 and 2 and dissolved. After casting, hot rolling, intermediate annealing, foil rolling, washing, and annealing under vacuum at 490 ° C. for 4 hours were performed to produce an aluminum foil having a thickness of 0.1 mm. After that, a predetermined amount of the above element was applied by ion implantation to obtain various samples as electrode materials for electrolytic capacitors.
【００１５】続いて、上記の各種アルミニウム箔を、液
温５０℃の１％水酸化ナトリウムを含む処理浴中に２秒
間浸漬し、然る後液温８５℃の５％塩酸及び１５％硫酸
を含むエッチング液で電流密度２０Ａ／dm2 の直流電流
を通じて６０秒間の第１段エッチングを施した後、液温
８５℃の５％塩酸及び０．１％しゅう酸を含むエッチン
グ液で電流密度５Ａ／dm2 の直流電流を通じて８分間の
第２段エッチングを施した。Subsequently, the above-mentioned various aluminum foils are immersed in a treatment bath containing 1% sodium hydroxide at a liquid temperature of 50 ° C. for 2 seconds, and then 5% hydrochloric acid and 15% sulfuric acid at a liquid temperature of 85 ° C. After performing a first-stage etching for 60 seconds with a DC current having a current density of 20 A / dm 2 using an etching solution containing 5% hydrochloric acid and 0.1% oxalic acid at a liquid temperature of 85 ° C., a current density of 5 A / dm 2 was used. The second stage etching was performed for 8 minutes by passing a direct current of dm 2 .
【００１６】そして、上記エッチド箔を３８０Ｖに化成
した後、各試料について箔基体とその表面に形成された
酸化皮膜との界面部における箔基体内層部（箔表面から
０．１μｍ以上に相当する深さの部位）に対するイオン
強度比を、一次イオン：Ａｒ＋、ビーム径：５００μ
ｍ、加速電圧：１０ｋＶ、電流：０．３μＡの分析条件
下で測定してその結果を第１表および第２表に示す一
方、それぞれの静電容量を測定し、比較例２８の試料の
静電容量を１００％とした場合との対比において他の各
種試料の静電容量比を求めその結果を第１表および第２
表に併記する。After the etched foil is converted to 380 V, the inner layer portion of the foil substrate (corresponding to 0.1 μm or more from the foil surface) at the interface between the foil substrate and the oxide film formed on the surface of each sample. The primary ion: Ar + , the beam diameter: 500 μ
m, acceleration voltage: 10 kV, current: 0.3 μA. The results are shown in Tables 1 and 2. On the other hand, the respective capacitances were measured. The capacitance ratios of other various samples were determined in comparison with the case where the capacitance was set to 100%, and the results were shown in Tables 1 and 2.
Also shown in the table.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】前記結果から分かるように、箔基体とその
表面に形成された酸化皮膜との界面部にエッチング核形
成元素のうちの１種または２種以上を本発明の規定量の
範囲で含有する電極箔は、過多にそれらの元素を含有す
る箔に較べ、静電容量の増大効果を有するものである。As can be seen from the above results, one or more of the etching nucleation elements are contained at the interface between the foil substrate and the oxide film formed on the surface thereof within the range specified in the present invention. The electrode foil has an effect of increasing the capacitance as compared with a foil containing these elements in excess.
【図１】 図１はこの発明にかかる電解コンデンサ電極
用アルミニウム箔の表面部位における検出イオン強度を
示すグラフである。FIG. 1 is a graph showing detected ionic strength at a surface portion of an aluminum foil for an electrolytic capacitor electrode according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−92518（ＪＰ，Ａ) 特開 昭61−117820（ＪＰ，Ａ) 特開 平４−137612（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01G 9/055 C22C 21/00 H01G 9/042 ────────────────────────────────────────────────── (5) References JP-A-59-92518 (JP, A) JP-A-61-117820 (JP, A) JP-A-4-137612 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01G 9/055 C22C 21/00 H01G 9/042
Claims (4)
つＣｕ、Ｓｉ、Ｚｎ、Ｍｎ、Ｇａ、Ｐ、Ｖ、Ｔｉ、Ｃ
ｒ、Ｎｉ、Ｔａ、Ｚｒ、Ｃ、Ｂｅ、Ｐｂ、Ｉｎ、希土類
元素のうち１種または２種以上の元素を含有するアルミ
ニウム箔からなり、上記元素が箔基体とその表面に形成
された酸化皮膜との界面部に濃化状態に含有されると共
に、該界面部における上記元素の濃度が箔基体内層部に
対するイオン強度比で１．２〜３０の範囲に設定されて
なることを特徴とする電解コンデンサ電極用アルミニウ
ム箔。An aluminum purity of 99.9% or more and Cu, Si, Zn, Mn, Ga, P, V, Ti, C
An aluminum foil containing one or more of r, Ni, Ta, Zr, C, Be, Pb, In, and rare earth elements, wherein the above elements are formed on a foil substrate and an oxide film formed on the surface thereof And the concentration of the element at the interface is set in the range of 1.2 to 30 in ionic strength ratio to the inner layer of the foil substrate. Aluminum foil for electrolytic capacitor electrodes.
つＣｕ、Ｓｉ、Ｚｎ、Ｍｎ、Ｇａのうち１種または２種
以上の元素を含有するアルミニウム箔からなり、上記元
素が箔基体とその表面に形成された酸化皮膜との界面部
に濃化状態に含有されると共に、該界面部における上記
元素の濃度が箔基体内層部に対するイオン強度比で１．
２〜３０の範囲に設定され、かつ箔表面から厚さ０．１
μｍまでの箔表層部を除いた箔内部に上記元素が３〜６
０ｐｐｍの範囲に含有されてなることを特徴とする電解
コンデンサ電極用アルミニウム箔。2. An aluminum foil having an aluminum purity of 99.9% or more and containing one or more elements of Cu, Si, Zn, Mn, and Ga, wherein said elements are a foil substrate and its surface. Is contained in a concentrated state at the interface with the oxide film formed on the foil substrate, and the concentration of the element at the interface is 1.
It is set in the range of 2 to 30 and has a thickness of 0.1 from the foil surface.
The above element is 3 to 6 inside the foil except for the foil surface layer up to μm.
An aluminum foil for an electrolytic capacitor electrode, which is contained in a range of 0 ppm.
つＰ、Ｖ、Ｔｉ、Ｃｒ、Ｎｉ、Ｔａ、Ｚｒ、Ｃ、Ｂｅの
うち１種または２種以上の元素を含有するアルミニウム
箔からなり、上記元素が箔基体とその表面に形成された
酸化皮膜との界面部に濃化状態に含有されると共に、該
界面部における上記元素の濃度が箔基体内層部に対する
イオン強度比で１．２〜３０の範囲に設定され、かつ箔
表面から厚さ０．１μｍまでの箔表層部を除いた箔内部
に上記元素が１〜４０ｐｐｍの範囲に含有されてなるこ
とを特徴とする電解コンデンサ電極用アルミニウム箔。3. An aluminum foil having an aluminum purity of 99.9% or more and containing one or more elements of P, V, Ti, Cr, Ni, Ta, Zr, C and Be, The above element is contained in a concentrated state at the interface between the foil substrate and the oxide film formed on the surface thereof, and the concentration of the element at the interface is 1.2% in terms of ionic strength to the inner layer of the foil substrate. For the electrolytic capacitor electrode, characterized in that the above element is contained in the range of 1 to 40 ppm in the foil except for the foil surface layer portion from the foil surface to the thickness of 0.1 μm, which is set in the range of from 30 to 30 μm. Aluminum foil.
かつＰｂ、Ｉｎ、希土類元素のうち１種または２種以上
の元素を含有するアルミニウム箔からなり、上記元素が
箔基体とその表面に形成された酸化皮膜との界面部に濃
化状態に含有されると共に、該界面部における上記元素
の濃度が箔基体内層部に対するイオン強度比で１．２〜
３０の範囲に設定され、かつ箔表面から厚さ０．１μｍ
までの箔表層部を除いた箔内部に上記元素が０．０１〜
３ｐｐｍの範囲に含有されてなることを特徴とする電解
コンデンサ電極用アルミニウム箔。4. An aluminum foil having an aluminum purity of 99.9% or more and containing one or more of Pb, In and rare earth elements, said elements being formed on the foil substrate and its surface. Is contained in a concentrated state at the interface with the oxidized film, and the concentration of the element at the interface is in the range of 1.2 to ionic strength relative to the inner layer of the foil substrate.
30 and 0.1 μm thick from the foil surface
The above elements are contained in the foil except for the surface layer of
An aluminum foil for an electrolytic capacitor electrode, wherein the aluminum foil is contained in a range of 3 ppm.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02401401A JP3130056B2 (en) | 1990-12-11 | 1990-12-11 | Aluminum foil for electrolytic capacitor electrodes |
| DE69118131T DE69118131T2 (en) | 1990-12-11 | 1991-12-04 | Aluminum foil like electrodes of electrolytic capacitor |
| EP91311298A EP0490574B1 (en) | 1990-12-11 | 1991-12-04 | Aluminum foil as electrolytic condenser electrodes |
| KR1019910022543A KR950013775B1 (en) | 1990-12-11 | 1991-12-10 | Aluminium foil for electrolytic capacitor |
| CN 91112795 CN1027718C (en) | 1990-12-11 | 1991-12-11 | Aluminum foil for electrolytic capacitor electrode |
| TW080109934A TW198122B (en) | 1990-12-11 | 1991-12-18 | |
| US08/304,261 US5518823A (en) | 1990-12-11 | 1994-09-12 | Aluminum foil as electrolytic condenser electrodes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02401401A JP3130056B2 (en) | 1990-12-11 | 1990-12-11 | Aluminum foil for electrolytic capacitor electrodes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04213812A JPH04213812A (en) | 1992-08-04 |
| JP3130056B2 true JP3130056B2 (en) | 2001-01-31 |
Family
ID=18511233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02401401A Expired - Fee Related JP3130056B2 (en) | 1990-12-11 | 1990-12-11 | Aluminum foil for electrolytic capacitor electrodes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3130056B2 (en) |
-
1990
- 1990-12-11 JP JP02401401A patent/JP3130056B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04213812A (en) | 1992-08-04 |
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