JP4465521B2 - Manufacturing method of aluminum alloy sheet for electrolytic capacitor - Google Patents
Manufacturing method of aluminum alloy sheet for electrolytic capacitor Download PDFInfo
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本発明は、高純度のアルミニウム母材にAｌを除く弁作用金属粉末を均一に分散させた電解コンデンサ用アルミニウム合金薄板の製造方法であって、該電解コンデンサ用アルミニウム合金薄板はエッチング処理を施して穿孔し、表面積を拡大してから誘電酸化物層を形成することによって、静電容量（C）と化成皮膜耐電圧（V）の積（以後CV積という）が高く、電子、電気機器の小型化、薄型化に適した電解コンデンサ用アルミニウム合金薄板の製造方法に関する。 The present invention relates to a method for producing an aluminum alloy sheet for an electrolytic capacitor in which a valve action metal powder excluding Al is uniformly dispersed in a high-purity aluminum base material . The aluminum alloy sheet for an electrolytic capacitor is subjected to an etching treatment. By forming a dielectric oxide layer after perforating and enlarging the surface area, the product of capacitance (C) and conversion film withstand voltage (V) (hereinafter referred to as CV product) is high, and the size of electronic and electrical equipment is small. The present invention relates to a method of manufacturing an aluminum thin plate for an electrolytic capacitor suitable for making the thickness and thickness thinner.
電解コンデンサ用アルミニウム薄板は通常、純度99.9％以上のアルミニウム溶湯を半連続鋳造によってスラブとし、更に面削、均質化処理、熱間圧延、必要に応じて中間焼鈍、冷間圧延を経て製品厚さに仕上げられる。その後、コンデンサメーカーによってエッチングと称する工程で穿孔して表面積を拡大し、化成工程によって誘電体皮膜を表面に形成して電解コンデンサ用の薄板とされる。 The aluminum sheet for electrolytic capacitors is usually made into a slab by semi-continuous casting of molten aluminum with a purity of 99.9% or more, and further undergoes chamfering, homogenization treatment, hot rolling, intermediate annealing as needed, and product thickness after cold rolling. Finished. Thereafter, a capacitor manufacturer drills in a process called etching to increase the surface area, and a chemical film forms a dielectric film on the surface to form a thin plate for an electrolytic capacitor.
近年、コンデンサの小型・高容量化の要求と共にエッチング技術が大幅に進歩し、化成電圧100Ｖ以下の低圧用途では、エッチングによる表面倍率が100倍を超え、化成皮膜研究の進歩も合わせてCV積が著しく増大してきた。しかしながら、現実のエッチング倍率には限界が有り、また、Al2 O3の誘電率は9程度で、Alを除く他の弁作用金属、即ちTi、Ta、Zr、Hf、Nbと比較して大きな値ではない。例えば、TiO2の誘電率は66、ZrO2が31、Nb2O5が47、HfO2が41、Ta2O5は25であり、アルミニウム製コンデンサのCV積を飛躍的に増加させるには、Al2 O3よりも誘電率の高い他の誘電体を利用することが有効である。 In recent years, the etching technology has greatly advanced along with the demand for smaller and higher capacity capacitors. For low-voltage applications with a conversion voltage of 100 V or less, the surface magnification by etching exceeds 100 times, and the CV product has increased along with advances in conversion coating research. It has increased significantly. However, there is a limit to the actual etching magnification, and the dielectric constant of Al 2 O 3 is about 9, which is larger than other valve action metals excluding Al, that is, Ti, Ta, Zr, Hf, Nb. Not a value. For example, the dielectric constant of TiO 2 is 66, ZrO 2 is 31, Nb 2 O 5 is 47, HfO 2 is 41, and Ta 2 O 5 is 25. To increase the CV product of aluminum capacitors dramatically It is effective to use another dielectric having a dielectric constant higher than that of Al 2 O 3 .
たとえば、特開平1-124212号公報には，弁作用金属であるTi、Ta、Zr、Hf、Nbの一種または複数種をアルミニウム溶湯に溶解して合金化し、鋳造に際し急冷凝固速度をコントロールして金属間化合物サイズを定め、化成電圧に即したエッチングを可能として、CV積の大きな電解コンデンサ用アルミニウム合金電極を提案している。
また、特開昭53-40605号公報には、アルミニウム粉末にAｌを除く弁作用金属粉末を均一に混合調整した後、該混合粉末を加圧成形して混合粉末の多孔質体とし、しかる後に該多孔質体に誘電酸化物層を形成させて静電容量の高い電解コンデンサを得ようとする技術が提案されている。
Japanese Patent Laid-Open No. 53-40605 discloses a method of uniformly mixing aluminum powder with a valve action metal powder excluding Al, and then pressing the mixed powder to form a porous body of the mixed powder. There has been proposed a technique for forming an electrolytic capacitor having a high capacitance by forming a dielectric oxide layer on the porous body.
前記特開平1-124212号公報記載の技術は、凝固速度をコントロールして金属間化合物サイズを定めるのでサイズの分布範囲が大きく一定せず、しかもAlを除く弁作用金属は融点が1700〜3000℃と高いために溶解させるにはかなり高温に加熱溶製しなくてはならない問題点があり、しかも加工硬化によって薄板までの成形加工が困難である。
また、前記特開昭53-40605号公報記載の技術は、未充填空隙部分の多い多孔質体に誘電酸化物層を形成してコンデンサとするものであるから、CV積は本発明のコンデンサと比較して１/３以下と低いものである。この多孔質体にエッチング処理を施して穿孔し、表面積を拡大しようとすると表面の溶解が不安定で均一な穿孔ができず、逆にCV積を下げてしまう。
The technique described in the above-mentioned Japanese Patent Application Laid-Open No. 1-124212 determines the intermetallic compound size by controlling the solidification rate, so that the size distribution range is not largely constant, and the valve action metal excluding Al has a melting point of 1700 to 3000 ° C. For this reason, there is a problem that it must be heated and melted at a considerably high temperature for dissolution, and it is difficult to form a thin plate by work hardening.
In addition, since the technique described in the above-mentioned Japanese Patent Application Laid-Open No. 53-40605 is a capacitor by forming a dielectric oxide layer on a porous body having many unfilled voids, the CV product is the same as that of the capacitor of the present invention. In comparison, it is as low as 1/3 or less. If this porous body is perforated by etching, and the surface area is increased, the surface dissolution is unstable and uniform perforation cannot be achieved, and the CV product is lowered.
即ち本発明の目的は、エッチング処理を施して穿孔し表面積を拡大してから誘電酸化物層を形成することによって、高いＣＶ積の得られる弁作用金属粉末を均一に分散含有させた電解コンデンサ用アルミニウム合金薄板および積層薄板を製造しようとするものである。 That is, the object of the present invention is for an electrolytic capacitor in which a valve action metal powder having a high CV product is uniformly dispersed and contained by forming a dielectric oxide layer after performing perforation by etching and expanding the surface area. It is intended to produce aluminum alloy sheets and laminated sheets.
発明者らは上記問題点を検討した結果、Alを除く弁作用金属を含有するアルミニウム合金溶湯の凝固速度をコントロールして金属間化合物サイズを定める替わりに，アルミニウム母材を高純度アルミニウムとし、このような高純度アルミニウム母材中に含有させる前記弁作用金属として微細粉末を用いた場合は、弁作用金属のサイズ管理が容易で、サイズ範囲を極端に狭くすることも可能であり、しかも高温溶製が不要であることを見出した。
さらに母材として高純度アルミニウム粉末を用いると共に強度に塑性変形させて得られた薄板は、エッチング処理で穿孔し表面積の拡大ができることを見出して本発明を完成したものである。
As a result of studying the above problems, the inventors determined that the aluminum base material was made of high-purity aluminum instead of determining the size of the intermetallic compound by controlling the solidification rate of the molten aluminum alloy containing the valve action metal excluding Al. When a fine powder is used as the valve metal contained in such a high-purity aluminum base material, the size of the valve metal can be easily controlled, the size range can be extremely narrow, and high-temperature melting can be achieved. It was found that there is no need for manufacturing.
Further, the present invention has been completed by finding that a thin plate obtained by using high-purity aluminum powder as a base material and plastically deforming to a high strength can be perforated by an etching process to increase the surface area.
即ち第一の発明は、製造されたアルミニウム合金薄板にエッチング処理を施して穿孔し、表面積を拡大してから誘電酸化物層を形成する工程に供する電解コンデンサ用アルミニウム合金薄板の製造方法であって、純度99.9％のアルミニウム粉末に、Alを除く弁作用金属の少なくとも一種の粉末であってその粒径が30〜50μmである粉末を重量で3〜90％均一に分散含有させた混合粉末体を、断面減少率で97.5％以上の塑性加工を施すことを特徴とする電解コンデンサ用アルミニウム合金薄板の製造方法である。これによって製造されるアルミニウム合金薄板は、強度に塑性変形してあるので、エッチング処理して穿孔し表面積の拡大ができ、爾後の化成処理で陽極酸化皮膜内に前記弁作用金属の誘電率の高い誘電体酸化物を生成させることができるので、CV積の高い電解コンデンサ用の薄板として使用できる。また、粉末のサイズ管理も容易である。
That is, the first invention is a method for producing an aluminum alloy thin plate for an electrolytic capacitor, which is subjected to a step of forming a dielectric oxide layer after subjecting the produced aluminum alloy thin plate to etching and perforating to increase the surface area. A mixed powder body obtained by uniformly dispersing 3 to 90% by weight of a powder of at least one kind of valve action metal excluding Al and having a particle size of 30 to 50 μm in an aluminum powder having a purity of 99.9% A method for producing an aluminum alloy thin plate for an electrolytic capacitor, characterized in that a plastic working with a cross-sectional reduction rate of 97.5% or more is performed. Since the aluminum alloy sheet produced by this is plastically deformed in strength, it can be perforated by etching treatment to increase the surface area, and the dielectric constant of the valve metal in the anodized film can be increased in the subsequent chemical conversion treatment. Since a dielectric oxide can be generated, it can be used as a thin plate for an electrolytic capacitor having a high CV product. In addition, the powder size can be easily managed.
Alを除く弁作用金属としては、酸化物として比較したときに、Alより誘電率の高いTi、Zr、Nb、Hf、Ta等であり、その粒径が30〜50μmである粉末として用いる。
本発明における電解コンデンサ用アルミニウム合金薄板の合金とは、粉末冶金で通常使用する用語に従うもので、Aｌを除く弁作用金属をAｌ溶湯に溶解して合金化し、鋳造法で鋳造して得られたものではなく、アルミニウム母材に弁作用金属粉末が分散している複合材的のようなものである。
The valve action metal excluding Al is Ti, Zr, Nb, Hf, Ta or the like having a dielectric constant higher than that of Al when compared as an oxide, and is used as a powder having a particle size of 30 to 50 μm.
The alloy of the aluminum alloy sheet for electrolytic capacitors in the present invention follows the terminology normally used in powder metallurgy, and is obtained by alloying a valve action metal other than Al by melting it in molten Al and casting it by a casting method. Instead, it is like a composite material in which valve metal powder is dispersed in an aluminum base material.
Alを除く前記弁作用金属粉末の含有量は電解コンデンサ用アルミニウム合金薄板重量に対して3〜90％とすることで、確実にCV値の高い電解コンデンサ用アルミニウム薄板とすることができる。さらに好ましい値は10％から40％である。 The content of the valve metal powders, except for Al than be 3-90% for aluminum alloy sheet weight electrolytic capacitor, can be reliably aluminum sheet for high CV value electrolytic capacitors. A more preferred value is 10% to 40%.
（削除） (Delete)
この発明では、アルミニウム粉末にAlを除く弁作用金属粉末を均一分散含有させた混合粉末体を圧延成形する際に、該アルミニウム粉末の純度を99.9%以上とすることで、混合粉末体を強度に塑性加工して得られた薄板は、エッチング処理して穿孔し表面積が拡大でき、高温に加熱溶製する必要がなく、エッチング処理で穿孔した後に化成処理し、誘電酸化物層を形成させることによって、CV積の高い電解コンデンサを得ることができる。
ここで、断面積減少率（θ）は以下のように計算され、混合粉末体を断面減少率95％以上の強度の塑性加工を施して電解コンデンサ用アルミニウム合金薄板とする。
混合粉末体の断面積：S
薄板の断面積：s
断面積減少率θ=[（S−ｓ）/S]×１００％
In this invention, when the mixed powder body in which the valve action metal powder excluding Al is uniformly dispersed and contained in the aluminum powder is formed by rolling, the purity of the aluminum powder is set to 99.9% or more, so that the mixed powder body is strengthened. The thin plate obtained by plastic working can be perforated by etching to increase the surface area, and it is not necessary to heat and melt at high temperature, and after forming by perforation by etching, chemical treatment is performed to form a dielectric oxide layer. An electrolytic capacitor with a high CV product can be obtained.
Here, the cross-sectional area reduction rate (θ) is calculated as follows, and the mixed powder body is subjected to plastic working having a cross-sectional reduction rate of 95% or more to obtain an aluminum alloy thin plate for an electrolytic capacitor.
Cross-sectional area of mixed powder: S
Thin plate cross-sectional area: s
Cross-sectional area reduction rate θ = [(S−s) / S] × 100%
第二の発明は、第一の発明により得られたアルミニウム合金薄板を、純度99.9％のアルミニウム芯材またはアルミニウム合金芯材の一側または両側に配することを特徴とする電解コンデンサ用アルミニウム合金積層薄板の製造方法である。このようにすることで、Alを除く弁作用金属粉末の使用量が少なく経済的な電解コンデンサ用アルミニウム合金積層薄板とすることができる。 The second invention is an aluminum alloy laminate for electrolytic capacitors, characterized in that the aluminum alloy thin plate obtained by the first invention is disposed on one side or both sides of an aluminum core material having a purity of 99.9% or an aluminum alloy core material. It is a manufacturing method of a thin plate. By doing in this way, it can be set as the economical aluminum alloy laminated thin plate for electrolytic capacitors with little usage-amount of the valve action metal powder except Al.
以上述べたように、本発明によれば、CV積が高く、電子、電気機器の小型化、薄型化に適した電解コンデンサ用のアルミニウム合金薄板を、溶製に際して高温に加熱する必要なしに製造することができる。 As described above , according to the present invention, an aluminum alloy thin plate for an electrolytic capacitor having a high CV product and suitable for downsizing and thinning of electronic and electrical equipment can be manufactured without the need to heat to high temperature during melting. can do.
電解コンデンサの静電容量Cは次式で与えられる。 The capacitance C of the electrolytic capacitor is given by the following equation.
C=8.855×10-8×ε×S/d (μF) C = 8.855 × 10-8 × ε × S / d (μF)
ここでεは誘電体の誘電率、Sは誘電体の表面積(cm2)、dは誘電体の厚さ(cm)である。CV積を高めるためにはCを大きくすればよい。例えばある化成電圧（d：一定）の時に、従来はCを高めるためにSを大きくする研究・開発がなされてきた。即ち、塩酸、硫酸、燐酸等、およびそれらの混酸溶液を用いた電気的、化学的エッチングによって表面積の拡大率が向上してきたのである。
しかしながら、99.98％程度の純度のアルミ薄板を用いた場合には、酸との反応でアルミ薄板の表面が溶解し、ピットの崩落によってCの向上には限りが有る。更に、より高い純度のアルミニウム薄板を用いようとすれば、著しい生産コストの上昇を招き、現実的ではない。
Here, ε is the dielectric constant of the dielectric, S is the surface area (cm 2 ) of the dielectric, and d is the thickness (cm) of the dielectric. To increase the CV product, C can be increased. For example, at a certain formation voltage (d: constant), research and development have been made to increase S to increase C. That is, the surface area enlargement ratio has been improved by electrical and chemical etching using hydrochloric acid, sulfuric acid, phosphoric acid, and the like, and mixed acid solutions thereof.
However, when an aluminum sheet with a purity of about 99.98% is used, the surface of the aluminum sheet is dissolved by reaction with acid, and the improvement of C is limited by the collapse of pits. Furthermore, if an aluminum sheet having a higher purity is used, the production cost is significantly increased, which is not realistic.
そこで本発明は、CV積の向上、即ち、Cの増大をεが9程度のAl2O3，に替わり、更に大きい他の弁作用金属、即ちTi、Zr、Nb、Hf、Ta等の粉末を用いることで達成しようとするものである。例えば、TiO2の誘電率は66、ZrO2が31、Nb2O5が47、HfO2が41、Ta2O5は25であり、エッチングによって穿孔し、表面積を拡大した後の化成処理時に、表面から露出した該弁作用金属が酸化されることで全体的なεを高め、Cを向上させる。
アルミニウム母材のAl純度を99.9％以上とするのは、薄板への成形加工が容易で、しかも該アルミニウム母材を粉末とし、混合体を前記の如く強塑性変形した薄板はエッチングピットが均一に穿孔でき、表面積を拡大できるためである。
Therefore, the present invention improves the CV product, that is, increases C by replacing Al 2 O 3 with ε of about 9, and further larger valve action metals, that is, powders of Ti, Zr, Nb, Hf, Ta, etc. This is what we want to achieve by using For example, the dielectric constant of TiO 2 is 66, ZrO 2 is 31, Nb 2 O 5 is 47, HfO 2 is 41, Ta 2 O 5 is 25. During chemical conversion treatment after drilling by etching and expanding the surface area The valve action metal exposed from the surface is oxidized to increase the overall ε and improve C.
The aluminum purity of the aluminum base material is set to 99.9% or more because it is easy to form into a thin plate, and the thin base plate made of the aluminum base material as a powder and strongly plastically deformed as described above has uniform etching pits. This is because it can be perforated and the surface area can be enlarged.
Alを除く弁作用金属は前述のようにAlより誘電率の高いTi、Zr、Nb、Hf、Ta等であって、該金属の粉末は、機械的粉砕、溶湯のアトマイズ冷却、急冷凝固帯の破砕等の公知の方法が採用でき、分級することでサイズ範囲を狭めることができる。粉末サイズは30〜50μmとすることでコスト高を避けつつCV積の高いアルミニウム薄板とすることができる。 The valve action metal excluding Al is Ti, Zr, Nb, Hf, Ta, etc. having a dielectric constant higher than that of Al as described above, and the metal powder is mechanically pulverized, atomized cooling of the molten metal, and rapidly solidified zone. Known methods such as crushing can be employed, and the size range can be narrowed by classification. By making the powder size 30 to 50 μm, it is possible to obtain an aluminum thin plate having a high CV product while avoiding high costs .
また、本発明では純度99.9％以上のアルミニウム母材に存在する前記弁作用金属が粉末であるから，該アルミニウム母材は母材中の不純物元素および該弁作用金属元素の固溶量、化合物に大きく左右されずに微細均一にエッチングされ、その後の化成処理で母材のAlと共に他の弁作用金属が酸化され、誘電率の高い皮膜を形成することができる。
なお、母材のアルミニウムと前記弁作用金属粉末界面は、Alと他の弁作用金属との金属間化合物の存在しない場合もあれば、薄板の製造過程の加熱乃至発熱で弁作用金属粉末周囲の一部で合金化あるいは金属間化合物を形成している場合もあるが、薄板への成形加工性およびアルミニウム母材のエッチングピットの均一性には大きな影響はなく、弁作用金属粉末周囲の界面の状態は特に限定しない。
前記Alを除く弁作用金属の含有量は、本発明に係るアルミニウム合金薄板全体に対して3〜90％である。3％未満では静電容量の向上効果が少なく、また90％を超えるとアルミニウム母材量が少なくなって、エッチング時に弁作用金属粉末の脱落が生じやすく、静電容量の低下の虞があるし、コストの観点から現実的ではない。好ましくは、10％から40％である。
Further, in the present invention, since the valve action metal present in an aluminum base material having a purity of 99.9% or more is a powder, the aluminum base material contains an impurity element in the base material, a solid solution amount of the valve action metal element, and a compound. The film is etched finely and uniformly without being greatly influenced, and the other valve action metal is oxidized together with the base material Al in the subsequent chemical conversion treatment, and a film having a high dielectric constant can be formed.
It should be noted that the base metal aluminum and the valve metal powder interface may not have an intermetallic compound of Al and other valve metal, or may be around the valve metal powder by heating or heat generation during the manufacturing process of the thin plate. In some cases, alloying or intermetallic compounds may be formed, but there is no significant effect on the formability of the thin plate and the uniformity of the etching pits in the aluminum base metal. The state is not particularly limited.
The content of valve metal other than said Al is 3 to 90 percent against the entire aluminum alloy sheet according to the present invention. If it is less than 3%, the effect of improving the capacitance is small, and if it exceeds 90%, the amount of the aluminum base material is small, and the valve metal powder is liable to fall off during etching, which may reduce the capacitance. Not realistic from a cost perspective. Preferably, it is 10% to 40%.
ここで薄板とは、箔を含む厚さの板で比較的薄い板を意味するものである。0.02〜0.9mm程度の板厚のものであるが、この範囲に限定するものではなく、上限の好ましい値は0.5mmが目安となる。 Here, the thin plate means a plate having a thickness including foil and a relatively thin plate. The thickness is about 0.02 to 0.9 mm, but the thickness is not limited to this range, and a preferable upper limit is 0.5 mm.
ここでAlを除く弁作用金属を粉末としたのは、前記弁作用金属がAlと比較し、融点が高いために合金化するには溶製時に高温溶解しなくてはならず、また該弁作用金属の含有量も高いことから、該弁作用金属とAlを共に溶解して合金化溶製した場合は、アルミニウム母材中に固溶する前記弁作用金属元素濃度が高くなって、加圧成形に際して加工硬化が甚だしく、特に圧延による薄板製造が著しく困難になるためである。 Here, the valve action metal excluding Al is powdered because the valve action metal has a higher melting point than Al, so that it must be melted at a high temperature during melting to be alloyed. Since the content of the working metal is also high, when the valve working metal and Al are melted together and alloyed and melted, the concentration of the valve working metal element dissolved in the aluminum base material is increased, and the pressure is increased. This is because the work-hardening is significant at the time of forming, and it is particularly difficult to produce a thin plate by rolling.
電解コンデンサ用アルミニウム合金箔は、エッチングに際して機械的強度および通電性を確保するために，エッチング後に全薄板厚さの10％から90％の部分が芯金として残される。この部分は前記弁作用金属粉末を含有している合金である必要はないから、経済性の面からこの芯金に相当する部分を純度99.9％以上のアルミニウム芯材またはアルミニウム合金芯材とし、該芯材の一側または両側に本発明の電解コンデンサ用アルミニウム合金薄板を設けて積層薄板とする。一側または両側に設ける本発明の電解コンデンサ用アルミニウム薄板の好ましい厚さは、積層薄板全体の厚さの10％から90％である。
ここで芯材のアルミニウムは純度99.9%以上のアルミニウムをいう。また芯材のアルミニウム合金は0.1%を超えるAl以外の元素を含有するアルミニウムをいう。
In the aluminum alloy foil for electrolytic capacitors, a portion of 10% to 90% of the total thin plate thickness is left as a metal core after etching in order to ensure mechanical strength and electrical conductivity during etching. Since this part does not need to be an alloy containing the valve action metal powder, the part corresponding to the core metal is made an aluminum core material or aluminum alloy core material with a purity of 99.9% or more from the economical aspect, The aluminum alloy thin plate for electrolytic capacitors of the present invention is provided on one side or both sides of the core material to form a laminated thin plate. The preferable thickness of the aluminum sheet for electrolytic capacitors of the present invention provided on one side or both sides is 10% to 90% of the total thickness of the laminated sheet.
Here, the core aluminum refers to aluminum having a purity of 99.9% or more. The aluminum alloy of the core material is aluminum containing more than 0.1% of elements other than Al.
前記積層薄板において、リーク電流低減の要求が特に厳しい場合に対応するためには純度99.9％以上のアルミニウムの芯材を用いることが好ましい。一方機械的強度が要求される場合には例えばA3003やA5754等のアルミニウム合金の芯材を用いることが好ましい。これらはクラッド鋳造やクラッド圧延で得られるが、本願はそれら製造手法には限定されない。 In the laminated thin plate, it is preferable to use an aluminum core material having a purity of 99.9% or more in order to cope with a case where the demand for leakage current reduction is particularly severe. On the other hand, when mechanical strength is required, it is preferable to use an aluminum alloy core material such as A3003 or A5754. These can be obtained by clad casting or clad rolling, but the present application is not limited to these manufacturing methods.
次に電解コンデンサ用アルミニウム合金薄板の好ましい製造方法について説明する。
Alを除く弁作用金属粉末を純度99.9％以上のアルミニウム母材中に均一に混合させるには、該アルミニウム粉末と該弁作用金属粉末とを機械的に混ぜ合わせるか、またはノズルから粉末を噴霧して混ぜ合わせるか等の方法で達成できる。均一に混合された混合粉末は型に入れて好ましい形状に焼結するか、或いは容器にいれて混合粉末体とする。
Next, the preferable manufacturing method of the aluminum alloy thin plate for electrolytic capacitors is demonstrated.
In order to uniformly mix the valve metal powder excluding Al into an aluminum base material having a purity of 99.9% or more , the aluminum powder and the valve metal powder are mechanically mixed or sprayed from a nozzle. This can be achieved by mixing them together. The uniformly mixed powder is put into a mold and sintered into a preferable shape, or put into a container to form a mixed powder body.
前記のようにして得られた混合粉末体は、金型プレス成形、押出成形等で所定の好ましい形状とされ、必要により圧延して薄板に成形される。この場合混合粉末体の断面積減少率が高く加工し難いときは、適宜焼鈍して薄板に加工する。 The mixed powder obtained as described above is formed into a predetermined preferable shape by die press molding, extrusion molding or the like, and is rolled into a thin plate if necessary. In this case, when the cross-sectional area reduction rate of the mixed powder body is high and difficult to process, it is appropriately annealed and processed into a thin plate.
前記混合粉末体がビレット形状で焼結されているがサイズの大きい形状の場合は加工硬化を抑制するため、また焼結されていない場合は粉末相互の金属結合を確実なものとするために、該混合粉末体を300℃から600℃の範囲に予備加熱して押出し加工し、次工程の圧延のためにフラットバーの板状に加工する。この押出加工で混合粉末体が焼結されていない場合は、前記弁作用金属粉末はアルミニウム母材と互いに金属結合し、爾後の圧延加工で確実に薄板に加工することで強度の高い薄板とすることができ、また高温に加熱溶製する必要がなく、CV積の高い電解コンデンサを得ることができる。 In order to suppress work hardening when the mixed powder body is sintered in a billet shape but has a large size, and to ensure metal bonding between the powders when not sintered, The mixed powder body is preheated in the range of 300 ° C. to 600 ° C., extruded, and processed into a flat bar plate for the next rolling process. When the mixed powder body is not sintered by this extrusion process, the valve action metal powder is metal-bonded to the aluminum base material, and is processed into a thin plate by rolling after the rolling to make a thin plate with high strength. In addition, there is no need to heat and melt at a high temperature, and an electrolytic capacitor having a high CV product can be obtained.
該混合粉末体が焼結されたものであって、サイズが小さく、加工率が低い場合は300℃未満の低温で押出し加工することができる。混合粉末が直接圧延できる場合は、その大きさによって混合粉末体を冷間乃至熱間で更に薄い板状に圧延する。爾後この薄板を必要により中間焼鈍を施して冷間圧延して薄板とする。この混合粉末体の加工率は、混合粉末体の断面積減少率で表記すれば95％以上の塑性加工を施すことによって、得られた薄板の組織は粉末の未充填部分が実質的に無くなり、エッチング処理してもピットの崩落が無く、表面積の拡大が可能となる。 When the mixed powder is sintered and has a small size and a low processing rate, it can be extruded at a low temperature of less than 300 ° C. When the mixed powder can be directly rolled, the mixed powder body is rolled into a thinner plate shape depending on its size, from cold to hot. After this, the thin plate is subjected to intermediate annealing if necessary and cold-rolled to obtain a thin plate. If the processing rate of this mixed powder body is expressed by the reduction rate of the cross-sectional area of the mixed powder body, by applying a plastic processing of 95% or more , the resulting thin plate structure is substantially free of unfilled portions of powder, Even if the etching process is performed, the pits are not collapsed and the surface area can be increased .
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このようにして製造された薄板は、必要に応じて最終焼鈍が施されて電解コンデンサ用アルミニウム合金薄板とされる。この製造方法も高温に加熱溶製する必要がなく、CV積の高い電解コンデンサを得ることができる。
前記押出しまたは圧延に供される被加工材の加熱温度が600℃を超えると酸化膜の著しい成長によって薄板のエッチング時に未エッチ部が発生して性能が低下するので避けることが好ましい。
The thin plate produced in this manner is subjected to final annealing as necessary to obtain an aluminum alloy thin plate for electrolytic capacitors. This manufacturing method also does not require heating and melting at a high temperature, and an electrolytic capacitor having a high CV product can be obtained.
When the heating temperature of the workpiece to be subjected to the extrusion or rolling exceeds 600 ° C., it is preferable to avoid an unetched portion at the time of etching the thin plate due to the remarkable growth of the oxide film, which deteriorates the performance.
特に本発明は母材が純度99.9％以上の高純度アルミニウムであるために加工硬化度が低く、前記弁作用金属粉末サイズにもよるが、Alを除く前記弁作用金属粉末サイズ程度の薄板厚さまで容易に圧延できると共にエッチング工程で均一なピットを穿孔することができる。
なお薄板のエッチングピットを均一にする目的で、各工程間で、必要に応じて酸やアルカリ、溶剤等で脱脂処理を行って、圧延面を清浄に保つこともできる。また、薄板の機械的強度調整のため、冷間圧延途中や薄板加工後に焼鈍を施すこともできる。その時の温度は250℃から550℃の範囲が好ましい。薄板の厚さは用途に応じて決定されるが、0.9mm以下、好ましくは0.02mmから0.5mmの間で適宜選択される。
In particular, in the present invention, since the base material is high-purity aluminum having a purity of 99.9% or more, the work hardening degree is low, and depending on the size of the valve metal powder, the thickness of the metal plate is about the same as the valve metal powder size excluding Al. It can be rolled easily and uniform pits can be drilled in the etching process.
For the purpose of making the etching pits of the thin plate uniform, the rolled surface can be kept clean by performing a degreasing treatment with an acid, an alkali, a solvent or the like as necessary between the respective steps. Also, annealing can be performed during cold rolling or after thin plate processing for adjusting the mechanical strength of the thin plate. The temperature at that time is preferably in the range of 250 ° C to 550 ° C. The thickness of the thin plate is determined according to the application, but is appropriately selected from 0.9 mm or less, preferably between 0.02 mm and 0.5 mm.
純度99.98％で平均粒径50μmのAl粉末とTi、Zr、Nb、Hf、Taのそれぞれの粉末を重量比で25％均一に混合して混合粉末体とし、該混合粉末体を焼結して200mmφのビレットを作製した。なお、弁金属粉末の粒径は分級によってそれぞれ30μmから50μmの範囲のもの（試料番号１〜５）と、約30μmから70μmの範囲のもの（試料番号７＝比較例５）を用いた。 Al powder with a purity of 99.98% and an average particle size of 50μm and each powder of Ti, Zr, Nb, Hf, and Ta are mixed uniformly by 25% by weight to form a mixed powder body, and the mixed powder body is sintered. A billet of 200 mmφ was produced. The particle diameter of the valve metal powder was 30 μm to 50 μm (sample number 1 to 5) and about 30 μm to 70 μm (sample number 7 = Comparative Example 5 ).
これらを400℃に予備加熱後、厚さ10mm×幅200mmのフラットバーに押出加工し、該フラットバーを冷間圧延によって厚さ1mmの薄板に圧延した後、芯材に厚さ1mmのAl純度99.98％のアルミニウム薄板を用いて3層のクラッド圧延することにより3層のクラッド板を得た。更に該3層のクラッド板を冷間圧延して厚さ100μm×幅200mmの積層薄板とした。
表層の厚さは35μm、芯材は30μmであった。断面積減少率は99.98％である。
このようにして製造された積層薄板を下記に示す電解エッチング条件でエッチングし、50g/リットル、60℃のアジピン酸アンモニウム溶液中で20Vに化成後特性を調べた結果を表１に示す。
These were preheated to 400 ° C, extruded into a flat bar with a thickness of 10 mm × width 200 mm, the flat bar was rolled into a thin plate with a thickness of 1 mm by cold rolling, and then the Al purity of the core with a thickness of 1 mm was obtained. A three-layer clad plate was obtained by rolling a three-layer clad using a 99.98% aluminum thin plate. Further, the three-layer clad plate was cold-rolled to obtain a laminated thin plate having a thickness of 100 μm × width of 200 mm.
The thickness of the surface layer was 35 μm and the core material was 30 μm. The cross-sectional area reduction rate is 99.98%.
Table 1 shows the results obtained by etching the laminated thin plate thus produced under the electrolytic etching conditions shown below and examining the properties after conversion to 20 V in an ammonium adipate solution at 50 g / liter and 60 ° C.
<電解エッチング条件>
液組成 ：４N HCl、0.1N Al3+、0.2N H2SO4、液温２５℃
電解波形 ： 正弦波交流、周波数50Hｚ
電流密度 ： 150mA/cm2
電解時間 ： ９００ｓ
<Electrolytic etching conditions>
Liquid composition: 4N HCl, 0.1N Al 3+ , 0.2NH 2 SO 4 , liquid temperature 25 ° C.
Electrolytic waveform: Sine wave AC, frequency 50Hz
Current density: 150mA / cm 2
Electrolysis time: 900s
実施例１と同様のAｌ粉末とTi粉末を用い同じ割合で混合粉末体とし、該混合粉末体を焼結して50mmφのビレットを作製した。これを400℃に予備加熱後、厚さ10mm×幅50mmのフラットバーに押出加工し、該フラットバーを冷間圧延によって厚さ1mm×幅50mmの薄板に圧延（試料番号１１）した。断面積減少率は97.5％である。
この薄板を実施例１と同じ条件でエッチングおよび化成処理し、特性を調べた結果を表１に示す。
The same Al powder and Ti powder as in Example 1 were used to form a mixed powder body at the same ratio, and the mixed powder body was sintered to prepare a 50 mmφ billet . This was preheated to 400 ° C., and then extruded into a flat bar having a thickness of 10 mm × width 50 mm, and the flat bar was rolled into a thin plate having a thickness of 1 mm × width 50 mm by cold rolling (sample number 11). The cross-sectional area reduction rate is 97.5%.
Table 1 shows the results of etching and chemical conversion treatment of this thin plate under the same conditions as in Example 1 and examining the characteristics.
「比較例１」
純度99.98％の従来製造法による市販アルミニウム箔（試料番号６）を用い、実施例１と同様の電解エッチング条件および化成条件で処理し特性を調べた結果を表１に示す。
"Comparative Example 1"
Table 1 shows the results of examining the characteristics by using a commercially available aluminum foil (sample No. 6) having a purity of 99.98% under the same electrolytic etching conditions and chemical conversion conditions as in Example 1.
「比較例２」
実施例１と同様のAｌ粉末とTi粉末を用い、同じ割合で混合粉末体とし、次いで焼結後断面積減少率30％で加圧成形して誘電酸化物層が形成できる程度の多孔質体（試料番号８）とした。このようにして製造された多孔質体を実施例１と同様の条件で電解エッチングした。その結果を表１に示す。
“Comparative Example 2”
A porous body that can form a dielectric oxide layer by using Al powder and Ti powder similar to those in Example 1 to form a mixed powder body at the same ratio, and then press-molding with a 30% reduction in cross-sectional area after sintering. (Sample No. 8). The porous body thus produced was electrolytically etched under the same conditions as in Example 1. The results are shown in Table 1.
「比較例３」
比較例２と同じ条件で製造した多孔質体に、脱落が生じない程度の条件でエッチングし（試料番号９）、実施例１と同じ条件で化成処理し、特性を調べた結果を表１に示す。
“Comparative Example 3”
The porous body manufactured under the same conditions as in Comparative Example 2 was etched under conditions that did not cause dropping (Sample No. 9), subjected to chemical conversion treatment under the same conditions as in Example 1, and the results of examining the characteristics are shown in Table 1. Show.
「比較例４」
純度99％で平均粒径50μmのAｌ粉末を用い、実施例１と同様の条件で厚さ１mmの薄板に圧延した後、更に圧延して厚さ0.25mmの薄板（試料番号１０）とした。断面積減少率は99.8%である。
このように製造された薄板を実施例１と同様の条件でエッチング処理した。結果を表１に示す。
“Comparative Example 4”
An Al powder having a purity of 99% and an average particle diameter of 50 μm was rolled into a 1 mm thick sheet under the same conditions as in Example 1, and then further rolled into a 0.25 mm thick sheet (Sample No. 10). The cross-sectional area reduction rate is 99.8%.
The thin plate thus produced was etched under the same conditions as in Example 1. The results are shown in Table 1.
表１の結果から、本発明例（試料番号１から５および11）はCV積が著しく高いことが判る。
なお、弁作用金属粉末サイズ範囲の狭い本発明例（試料番号１）は、サイズ範囲の広い比較例５（試料番号７）と比較してCV積が高いことが判る。
一方、従来箔を用いた比較例１（試料番号６）はCV積が低いことが判る。
断面積減少率が小さい多孔質体である比較例２（試料番号８）は、エッチング処理でピットの崩落を含む溶解減量が激しく、静電容量を測定できないことが判る。
純度99％のAｌ粉末を用いた比較例４（試料番号９）は、Aｌ粉末の純度が低く孔食の起点となるものが多く、エッチング処理で脱落を含む溶解減量が激しく、静電容量を測定できないことが判る。
From the results in Table 1, it can be seen that the inventive examples (sample numbers 1 to 5 and 11) have a remarkably high CV product.
In addition, it turns out that the example of this invention (sample number 1) with a narrow valve action metal powder size range has a high CV product compared with the comparative example 5 (sample number 7) with a wide size range.
On the other hand, it can be seen that Comparative Example 1 (Sample No. 6) using the conventional foil has a low CV product.
It can be seen that Comparative Example 2 (Sample No. 8), which is a porous body having a small cross-sectional area reduction rate, has a strong dissolution loss including pit collapse by the etching process, and the capacitance cannot be measured.
In Comparative Example 4 (Sample No. 9) using 99% pure Al powder, the purity of the Al powder is low, and many of them become the starting point of pitting corrosion. It turns out that it cannot be measured.
以上述べたように、本発明はCV積が高く、電子、電気機器の小型化、薄型化に適した電解コンデンサ用のアルミニウム合金箔であり、かつ溶製に際して高温に加熱する必要のない電解コンデンサ用のアルミニウム合金箔の製造方法であるから、産業上の利用可能性が高い発明であると理解される。 As described above, the present invention is an aluminum alloy foil for electrolytic capacitors that has a high CV product and is suitable for downsizing and thinning of electronic and electrical equipment, and does not require heating to a high temperature during melting. Therefore, it is understood that the present invention has a high industrial applicability.
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