JP2003071546A - Aluminum ingot, and continuous casting method therefor, and manufacturing method for aluminum foil for electrode of electrolytic capacitor using the aluminum ingot - Google Patents
Aluminum ingot, and continuous casting method therefor, and manufacturing method for aluminum foil for electrode of electrolytic capacitor using the aluminum ingotInfo
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- JP2003071546A JP2003071546A JP2001260732A JP2001260732A JP2003071546A JP 2003071546 A JP2003071546 A JP 2003071546A JP 2001260732 A JP2001260732 A JP 2001260732A JP 2001260732 A JP2001260732 A JP 2001260732A JP 2003071546 A JP2003071546 A JP 2003071546A
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- ingot
- aluminum
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、アルミニウム鋳塊
およびその連続鋳造方法ならびに前記アルミニウム鋳塊
を用いた電解コンデンサの電極用アルミニウム箔の製造
方法に関する。尚、本明細書において、アルミニウムの
連続鋳造方法には、鋳塊(スラブ)の鋳込み方向の長さが
最大で4〜6メートルであるアルミニウムの半連続鋳造
方法も含まれる。また、本明細書におけるアルミニウム
には、純アルミニウムはもとより、各種のアルミニウム
合金も含まれる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum ingot, a continuous casting method therefor, and a method for producing an aluminum foil for an electrode of an electrolytic capacitor using the aluminum ingot. In the present specification, the continuous aluminum casting method includes a semi-continuous aluminum casting method in which the length of the ingot (slab) in the casting direction is 4 to 6 meters at the maximum. Further, aluminum in the present specification includes not only pure aluminum but also various aluminum alloys.
【0002】[0002]
【従来の技術】中圧または高圧電解コンデンサに用いら
れる電極用アルミニウム箔は、アルミニウムからなる鋳
塊(スラブ)の連続鋳造、均質化処理、熱間圧延、冷間圧
延、および仕上げ(最終)焼鈍の各工程を経て製造されて
いる。係る工程を経ることにより、得られる電極用アル
ミニウム箔は、立方体方位(001)[100]の結晶粒
が鮮鋭に顕在化した金属組織となるようにされている。
また、上記立方体方位粒を一層鮮鋭に顕在化させるた
め、冷間圧延と仕上げ焼鈍との間において、更に中間焼
鈍および冷間圧延を行うことも試みられている。尚、上
記鋳塊の連続鋳造は、全体が金属製の水冷鋳型を用いた
連続鋳造法により行われる。また、上記(001)は結晶
粒の圧延面に平行な結晶面を、[100]は結晶粒の圧
延方向に平行な結晶軸を、ミラー指数で表示したもので
ある。2. Description of the Related Art Aluminum foil for electrodes used in medium or high voltage electrolytic capacitors is manufactured by continuously casting ingots (slabs) made of aluminum, homogenizing, hot rolling, cold rolling, and finishing (final) annealing. It is manufactured through each process. Through the steps described above, the obtained aluminum foil for an electrode has a metal structure in which crystal grains having a cubic orientation (001) [100] are sharply exposed.
Further, in order to make the cubic oriented grains more sharply visible, it has been attempted to further perform intermediate annealing and cold rolling between cold rolling and finish annealing. The continuous casting of the ingot is performed by a continuous casting method using a water-cooled mold made entirely of metal. Further, (001) represents the crystal plane parallel to the rolled surface of the crystal grain, and [100] represents the crystal axis parallel to the rolled direction of the crystal grain by the Miller index.
【0003】上記アルミニウム箔は、幅が約1000m
mのコイルにおける全領域において、上記立方体方位粒
が上述したように顕在化していることが求められてい
る。しかしながら、図4(A)に示すように、上記コイル
の幅方向におけるセンターからエッジ(縁)にわたる約幅
500mmのアルミニウム箔において、幅方向のエッジ
付近に上記立方体方位(001)[100]以外の結晶方
位(非立方体方位)の結晶粒が生成し残留する場合があ
る。尚、図4(A)は、上記アルミニウム箔の表面を、塩
酸:硝酸:弗酸を50:50:1の割合で調整した薬品
(腐食液)で溶解し、係る表面に対して垂直でない光を用
いて写真撮影したもの(模式的図面)を示す。この結果、
図4(A)中で立方体方位の結晶粒は黒色として、非立方
体方位の結晶粒は白色として表示されている。上記非立
方体方位の結晶粒は、面方位および軸方位の何れかまた
は双方にて、立方体方位(001)[100]から15度
を超える傾きを有している。この結果、上記コイルの幅
方向のエッジ付近では、幅方向のセンター付近に比べて
前述した顕在化のレベルが低くなる、という問題があっ
た。このため、上記コイル中における顕在化のバラツキ
により、追って前記コンデンサの電極用アルミニウム箔
とした場合、その特性が不均一になるため、信頼性を損
なう場合があった。The aluminum foil has a width of about 1000 m.
It is required that the cubic oriented grains are manifested as described above in the entire region of the coil of m. However, as shown in FIG. 4 (A), in an aluminum foil having a width of about 500 mm extending from the center to the edge in the width direction of the coil, the other than the cube orientation (001) [100] near the edge in the width direction. Crystal grains of crystal orientation (non-cubic orientation) may be generated and remain. In addition, FIG. 4 (A) shows a chemical prepared by adjusting the surface of the aluminum foil with hydrochloric acid: nitric acid: hydrofluoric acid at a ratio of 50: 50: 1.
A photograph (schematic drawing) taken with light that is dissolved in (corrosion liquid) and is not perpendicular to the surface is shown. As a result,
In FIG. 4 (A), crystal grains with a cubic orientation are shown as black, and crystal grains with a non-cube orientation are shown as white. The crystal grains in the non-cubic orientation have an inclination of more than 15 degrees from the cubic orientation (001) [100] in either or both of the plane orientation and the axial orientation. As a result, there is a problem in that the level of the above-mentioned manifestation becomes lower near the edge in the width direction of the coil as compared to near the center in the width direction. For this reason, when the aluminum foil for electrodes of the capacitor is subsequently used, the characteristics thereof become non-uniform due to the variation in manifestation in the coil, which may impair the reliability.
【0004】発明者らが鋭意研究した結果、前述した非
立方体方位の結晶粒が生成・残留する原因は、アルミニ
ウムを連続鋳造して得られる鋳塊(スラブ)における集合
組織の分布にあることを見出した。即ち、通常の連続鋳
造法により得られた鋳塊を鋳造方向と直角に切断し、露
出した切断面を塩酸:硝酸:弗酸を50:50:1の割
合に調整した薬品(腐食液)で溶解し、係る切断面に垂直
でない光を当てて写真撮影すると、現出する柱状晶にお
いて、その[100]軸が鋳造方向と平行なものは黒色
として、鋳造方向から15度を超えて傾いたものは白色
として映る。その結果、図4(B)に示すように、鋳造方
向と直交する切断面において、追って圧延時の幅方向の
エッジに相当する幅方向のエッジ(縁部)寄りでは白色に
映る柱状晶が比較的多く発達し、幅方向のセンター寄り
では黒色に映る柱状晶が比較的多く発達していたことが
判明した。これにより、前述した問題点は、上記鋳塊に
おける集合組織の不均一さが原因であることを突き止め
た。As a result of intensive studies by the inventors, it was found that the cause of the generation and retention of the above-mentioned non-cubic crystal grains is the distribution of the texture in the ingot (slab) obtained by continuously casting aluminum. I found it. That is, the ingot obtained by the normal continuous casting method was cut at a right angle to the casting direction, and the exposed cut surface was treated with a chemical (corrosion solution) adjusted to a ratio of hydrochloric acid: nitric acid: hydrofluoric acid of 50: 50: 1. When it was melted and photographed by shining light that was not perpendicular to the cut surface, the columnar crystals that appeared were those in which the [100] axis was parallel to the casting direction were black, and were inclined by more than 15 degrees from the casting direction. Objects appear white. As a result, as shown in FIG. 4 (B), in the cross section orthogonal to the casting direction, columnar crystals that appear white in the widthwise edges (edges) corresponding to the widthwise edges during rolling are compared later. It was found that a large number of columnar crystals that appeared black were relatively developed near the center in the width direction. From this, it was found that the above-mentioned problems were caused by the nonuniformity of the texture in the ingot.
【0005】[0005]
【発明が解決すべき課題】本発明は、以上にて説明した
従来の技術における問題点を解決し、鋳塊を箔コイルに
成形した際でも全領域で立方体方位粒が顕在化した金属
組織を有するアルミニウム鋳塊およびその連続鋳造方法
ならびに係る鋳塊を用いた電解コンデンサの電極用アル
ミニウム箔の製造方法を提供する、ことを課題とする。DISCLOSURE OF THE INVENTION The present invention solves the problems in the prior art described above and provides a metallographic structure in which cubic oriented grains are exposed in all regions even when an ingot is formed into a foil coil. It is an object of the present invention to provide an aluminum ingot and a continuous casting method thereof, and a method for manufacturing an aluminum foil for an electrode of an electrolytic capacitor using the ingot.
【0006】[0006]
【課題を解決するための手段】本発明は、上記課題を解
決するため、発明者らが鋭意研究の結果、アルミニウム
鋳塊を連続鋳造する際、[100]柱状晶を全領域で生
成および成長させる、ことに着目して成されたものであ
る。尚、[100]柱状晶は、その[100]軸が鋳造
方向とほぼ平行となる柱状晶を指す。即ち、本発明のア
ルミニウム鋳塊(請求項1)は、上端部および下端部を開
放した筒状の冷却鋳型の上端部からアルミニウムの溶湯
を供給しつつ冷却して凝固した鋳塊を下端部から引き下
ろし且つ冷却液を注加して連続鋳造されるアルミニウム
鋳塊であって、鋳造初期に核生成した結晶が柱状晶とし
て上方および内部方向にほぼ沿って成長し且つ定常部の
鋳塊の表面からの新たな結晶の核生成が生じていないと
共に、上記鋳塊における柱状晶の[100]軸が鋳造方
向とほぼ平行である、ことを特徴とする。尚、上記「ほ
ぼ平行」とは、柱状晶の[100]軸が鋳造方向と平行
であるかあるいは係る鋳造方向から±15度以内の傾き
を有することを指す。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted earnest research and as a result, when continuously casting an aluminum ingot, [100] columnar crystals are generated and grown in all regions. It was made paying attention to that. The [100] columnar crystal is a columnar crystal whose [100] axis is substantially parallel to the casting direction. That is, the aluminum ingot of the present invention (Claim 1) is an ingot which is cooled and solidified while supplying molten metal of aluminum from the upper end of a cylindrical cooling mold whose upper end and lower end are opened. An aluminum ingot which is continuously cast by pulling down and pouring a cooling liquid, in which crystals nucleated in the initial stage of casting grow as columnar crystals substantially along the upper direction and the inner direction, and from the surface of the ingot of the steady part. No new nucleation of crystals has occurred, and the [100] axis of the columnar crystals in the ingot is substantially parallel to the casting direction. The term “substantially parallel” means that the [100] axis of the columnar crystal is parallel to the casting direction or has an inclination within ± 15 degrees from the casting direction.
【0007】これによれば、上記冷却鋳型に供給された
アルミニウムの溶湯は、係る鋳型の内壁表面からは冷却
されず、鋳型の下端から斜め下向きに注加される冷却液
による冷却により凝固する。換言すれば、鋳型の内壁表
面では核生成が生じないため、係る鋳造操作を連続して
行い且つ冷却鋳型の下端部から順次引き下ろした鋳塊に
対し冷却液を注加することにより、[100]軸が鋳造
方向とほぼ平行である柱状晶を全体に形成したアルミニ
ウム鋳塊となっている。即ち、上記鋳塊においては、鋳
造初期の凝固時に核生成する結晶粒のうち、その[10
0]軸が鋳造方向(冷却鋳型の軸方向)とほぼ平行なもの
のみが成長して柱状晶となると共に、係る柱状晶は、全
体として鋳造方向に沿ってほぼ平行に成長すると共に、
本鋳塊(スラブ)の内側(中心部)に向かって成長してい
る。According to this, the molten aluminum supplied to the cooling mold is not cooled from the inner wall surface of the mold, but is solidified by the cooling liquid poured obliquely downward from the lower end of the mold. In other words, since nucleation does not occur on the surface of the inner wall of the mold, the casting operation is continuously performed, and the cooling liquid is poured into the ingot sequentially drawn from the lower end of the cooling mold, thereby [100] The ingot is an aluminum ingot having columnar crystals whose axes are substantially parallel to the casting direction. That is, in the ingot, among the crystal grains nucleated during solidification in the initial stage of casting, [10
0] axis grows substantially parallel to the casting direction (axial direction of the cooling mold) to form columnar crystals, and the columnar crystals grow as a whole substantially parallel to the casting direction, and
It grows toward the inside (center) of the ingot (slab).
【0008】尚、本明細書において、鋳造初期とは、後
述する定常条件による鋳造状態に至らない非定常条件で
鋳造を行っている時期を指す。また、上記[100]柱
状晶は、その[100]軸の向きが鋳造方向(冷却鋳型
の軸方向)と平行であるか、係る鋳造方向を中心にして
±15度以内の傾斜である結晶粒を指す。換言すると、
これらを除いたものが、非[100]柱状晶である。更
に、上記[100]柱状晶は、その軸方位と後述する圧
延方向にもなる鋳造方向との関係を表すものであり、圧
延時の圧延面と平行な面方位についてまで規定するもの
ではない。また、定常部とは、鋳塊(スラブ)の先端(下
端)を支持しつつ順次下降する下型(テーブル)の下降速
度および冷却液の給液量が定常条件となる時期を指す。
更に、以上の冷却液には、冷却水の他、冷却油なども含
まれる。加えて、本発明のアルミニウムの連続鋳造方法
には、電磁鋳造法、OCCプロセス、または発明者らが
提唱するシェルフリー鋳造法の何れを用いても良い。In the present specification, the term "initial stage of casting" refers to the period when casting is carried out under unsteady conditions that do not reach the casting state under steady conditions described later. In addition, the [100] columnar crystal is a crystal grain in which the direction of the [100] axis is parallel to the casting direction (axial direction of the cooling mold) or is inclined within ± 15 degrees around the casting direction. Refers to. In other words,
Those excluding these are non- [100] columnar crystals. Furthermore, the [100] columnar crystal represents the relationship between the axial orientation and the casting direction, which is also the rolling direction described later, and does not specify the plane orientation parallel to the rolling surface during rolling. Further, the steady portion refers to a time when the lowering speed of the lower die (table) that sequentially descends while supporting the tip (lower end) of the ingot (slab) and the supply amount of the cooling liquid are steady conditions.
Further, the above cooling liquid includes cooling oil as well as cooling water. In addition, the aluminum continuous casting method of the present invention may be either an electromagnetic casting method, an OCC process, or a shell-free casting method proposed by the inventors.
【0009】また、本発明のアルミニウム鋳塊の連続鋳
造方法(請求項2)は、上端部および下端部を開放した筒
状の冷却鋳型の上端部からアルミニウムの溶湯を供給す
ると共に、冷却して凝固した鋳塊を下端部から引き下ろ
し且つ冷却液を注加してアルミニウム鋳塊を連続鋳造す
る方法において、上記冷却鋳型の上端部における前記溶
湯注入側が、耐火性断熱材からなると共に、上記冷却鋳
型における冷却リングの鋳型長さ、鋳造速度、および冷
却液量の少なくとも1つ以上を調整することにより、上
記アルミニウムの溶湯の凝固開始点が上記耐火性断熱材
の領域内で生じる、を特徴とする。Further, in the method for continuously casting an aluminum ingot according to the present invention (claim 2), the molten aluminum is supplied and cooled from the upper end of a cylindrical cooling mold whose upper end and lower end are opened. In the method of pulling down the solidified ingot from the lower end and continuously casting an aluminum ingot by adding a cooling liquid, the molten metal injection side at the upper end of the cooling mold is made of a refractory heat insulating material, and the cooling mold By adjusting at least one of the mold length of the cooling ring, the casting speed, and the amount of the cooling liquid, the solidification start point of the molten aluminum is generated in the region of the refractory heat insulating material. .
【0010】これによれば、冷却鋳型の溶湯注入側が耐
火性断熱材により構成されているため、アルミニウムの
溶湯から上記鋳型を介する抜熱が抑制される。この結
果、溶湯からの抜熱は、冷却液により冷却される下方に
のみ向かうため、[100]軸が鋳造方向とほぼ平行な
柱状晶をアルミニウム鋳塊の全体で生成できる。即ち、
溶湯の凝固開始点を耐火性断熱材の領域(レベル)内にす
るため、冷却鋳型の冷却リングの鋳型長さを短くし、鋳
造速度を低め、あるいは冷却液量を増加するの少なくと
も何れかを調整することで、冷却鋳型からの抜熱を一層
抑制でき且つ下方への上記抜熱のみに制限し易くなる。
これらにより、鋳造の定常部において、鋳塊の表面から
の新たな結晶粒の核生成が抑制されるため、[100]
軸が鋳造方向とほぼ平行な柱状晶を全体に形成した鋳塊
を確実に得ることができる。尚、耐火性断熱材には、例
えば珪酸カルシウムなどが用いられる。According to this, since the molten metal injection side of the cooling mold is made of the refractory heat insulating material, heat removal from the molten aluminum through the mold is suppressed. As a result, the heat removal from the molten metal is directed only to the lower side where it is cooled by the cooling liquid, so that columnar crystals whose [100] axis is substantially parallel to the casting direction can be generated in the entire aluminum ingot. That is,
In order to make the solidification start point of the molten metal within the area (level) of the refractory heat insulating material, shorten the mold length of the cooling ring of the cooling mold, lower the casting speed, and / or increase the cooling liquid amount. By adjusting, the heat removal from the cooling mold can be further suppressed, and it becomes easy to limit only the above heat removal to the lower side.
These suppress nucleation of new crystal grains from the surface of the ingot in the steady part of casting, and thus [100]
It is possible to reliably obtain an ingot in which columnar crystals whose axes are substantially parallel to the casting direction are entirely formed. For the refractory heat insulating material, for example, calcium silicate or the like is used.
【0011】更に、本発明には、前記冷却鋳型の上端部
における溶湯注入側の耐火性断熱材の内側に、黒鉛また
はこれと同等の特性を有する鋳型面を形成すると共に、
前記アルミニウムの溶湯の凝固開始点が上記鋳型面にお
いて生じる、アルミニウム鋳塊の連続鋳造方法(請求項
3)も含まれる。これによれば、黒鉛からなる鋳型面ま
たは黒鉛と同等の固体潤滑特性を有する鋳型面がアルミ
ニウムの溶湯および鋳塊の表面に接触するため、断熱材
の劣化を防止しつつ上記鋳型を介する抜熱を一層抑制す
ることができる。しかも、上記黒鉛などからなる鋳型面
のレベル中で溶湯の凝固開始点が生じるため、鋳塊表面
における核生成が抑制され、鋳造方向にほぼ平行な[1
00]軸を持った下方からの柱状晶の成長が維持され
る。その結果、[100]軸が鋳造方向にほぼ平行な柱
状晶の成長を鋳造方向および内部方向に沿ったものに容
易に制御することが可能となると共に、非[100]柱
状晶の核生成が抑制されるため、鋳造方向とほぼ平行な
[100]軸を持った柱状晶を全体に形成したアルミニ
ウム鋳塊を容易に製造することができる。Furthermore, according to the present invention, graphite or a mold surface having characteristics equivalent to graphite is formed inside the refractory heat insulating material on the molten metal injection side at the upper end of the cooling mold.
A continuous casting method for aluminum ingots (claim 3) in which the solidification start point of the molten aluminum occurs on the mold surface is also included. According to this, since the mold surface made of graphite or the mold surface having the same solid lubricating property as graphite contacts the surface of the molten aluminum and the ingot, heat removal through the mold while preventing deterioration of the heat insulating material. Can be further suppressed. Moreover, since the starting point of solidification of the molten metal occurs at the level of the mold surface made of the above graphite or the like, nucleation on the surface of the ingot is suppressed and it is almost parallel to the casting direction [1
The growth of columnar crystals from below with the [00] axis is maintained. As a result, it becomes possible to easily control the growth of the columnar crystals whose [100] axis is substantially parallel to the casting direction along the casting direction and the inner direction, and at the same time, the nucleation of non- [100] columnar crystals occurs. Since it is suppressed, it is possible to easily manufacture an aluminum ingot in which columnar crystals each having a [100] axis substantially parallel to the casting direction are formed.
【0012】一方、本発明による電解コンデンサの電極
用アルミニウム箔の製造方法(請求項4)は、前記アルミ
ニウム鋳塊を均質化処理し、その後、係る鋳塊の上記鋳
造時の鋳造方向を圧延方向とする熱間圧延と冷間圧延と
を含む成形工程および仕上げ焼鈍を含む熱処理工程を施
す、ことを特徴とする。これによれば、前記[100]
軸が鋳造方向とほぼ平行な柱状晶を鋳塊全体に形成され
た上記鋳塊を均質化処理し、その後、上記鋳造方向に沿
った圧延方向(長手方向)の熱間圧延および冷間圧延など
の成形工程および仕上げ焼鈍などの熱処理工程が施され
る。上記成形工程の結果、箔コイルの全領域において、
均一な圧延集合組織が形成される。そして、仕上げ焼鈍
中において圧延集合組織から立方体方位の結晶粒が生成
するが、箔コイルの全領域において圧延集合組織が均一
であるため、係るコイルの全領域で均一に立方体方位の
結晶粒が顕在(鮮鋭)化する。従って、例えば静電容量な
どの特性が優れた電解コンデンサの電極用アルミニウム
箔を確実に製造することが可能となる。尚、均質化処理
には、単に熱間圧延前の加熱を目的に行う場合も含まれ
る。On the other hand, in the method for producing an aluminum foil for electrodes of an electrolytic capacitor according to the present invention (claim 4), the aluminum ingot is homogenized, and then the casting direction of the ingot at the time of the casting is set to the rolling direction. Forming process including hot rolling and cold rolling and heat treatment process including finish annealing. According to this, [100]
Homogenization treatment of the ingot in which the axis is almost parallel to the casting direction and columnar crystals formed in the entire ingot, and then hot rolling and cold rolling in the rolling direction (longitudinal direction) along the casting direction And a heat treatment step such as finish annealing. As a result of the molding process, in all areas of the foil coil,
A uniform rolling texture is formed. Then, during the finish annealing, cubic-oriented crystal grains are generated from the rolling texture, but since the rolling texture is uniform in the entire area of the foil coil, the cubic-oriented crystal grains appear uniformly in the entire area of the coil. Become sharp. Therefore, it is possible to reliably manufacture the aluminum foil for electrodes of the electrolytic capacitor having excellent characteristics such as capacitance. The homogenization treatment includes a case where the heating is simply performed before hot rolling.
【0013】また、本発明には、前記鋳塊は、前記冷間
圧延と仕上げ焼鈍との間において、中間焼鈍および仕上
げ冷間圧延を更に施される、電解コンデンサの電極用ア
ルミニウム箔の製造方法(請求項5)も含まれる。これに
よれば、中間焼鈍および仕上げ冷間圧延を更に行うこと
により、当初の冷間圧延による圧延集合組織から中間焼
鈍中において生成する不必要な非立方体方位の結晶粒が
仕上げ焼鈍中に十分に生成および成長しなくなる。この
結果、立方体方位の結晶粒が一層鮮鋭(顕在)化した電極
用アルミニウム箔を確実に製造することが可能となる。Further, according to the present invention, the ingot is further subjected to intermediate annealing and finish cold rolling between the cold rolling and finish annealing, a method for producing an aluminum foil for electrodes of electrolytic capacitors. (Claim 5) is also included. According to this, by further performing intermediate annealing and finish cold rolling, unnecessary non-cube-oriented crystal grains generated during intermediate annealing from the rolling texture of the initial cold rolling are sufficiently formed during finish annealing. It will stop producing and growing. As a result, it becomes possible to reliably manufacture the aluminum foil for electrodes in which the crystal grains in the cubic orientation are sharper (revealed).
【0014】[0014]
【発明の実施の形態】以下において、本発明の実施に好
適な形態を図面と共に説明する。図1は、本発明のアル
ミニウム鋳塊を得るための本発明による連続鋳造方法の
概略およびこれに用いる鋳造装置1を示す。係る鋳造装
置1は、シェルフリー鋳造法に専ら用いられるものであ
り、図1に示すように、平面視が矩形で上端部3および
下端部4が開放した中空部5を内側に有する筒状の水冷
鋳型(冷却鋳型)2と、この水冷鋳型2の中心軸付近に上
方から垂下するスパウト(注湯管)10と、水冷鋳型2の
下方において昇降自在に位置する下型16と、を備えて
いる。図1に示すように、水冷鋳型2は、その上端部3
寄りに配置され且つアルミニウムの溶湯Mの注入側であ
る耐火性断熱材6と、その下端部4寄りに配置され且つ
断面角形の中空部9を有する金属製の冷却リング8とか
らなる。尚、中空部5は、平面視で長方形を呈し、短辺
300〜600mm×長辺1000〜2000mmのサ
イズを有する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments for carrying out the present invention will be described with reference to the drawings. FIG. 1 shows an outline of a continuous casting method according to the present invention for obtaining an aluminum ingot of the present invention and a casting apparatus 1 used for the method. The casting apparatus 1 according to the present invention is used exclusively in the shell-free casting method, and as shown in FIG. 1, has a tubular shape having a rectangular shape in plan view and a hollow portion 5 having an open upper end 3 and a lower end 4 inside. A water-cooled mold (cooling mold) 2, a spout (pouring pipe) 10 hanging from above near the central axis of the water-cooled mold 2, and a lower mold 16 positioned below the water-cooled mold 2 so as to be vertically movable. There is. As shown in FIG. 1, the water-cooled mold 2 has an upper end 3
It comprises a refractory heat insulating material 6 which is located nearer to the side where the molten aluminum M is injected and a metal cooling ring 8 which is located nearer the lower end 4 thereof and has a hollow portion 9 having a square cross section. The hollow portion 5 has a rectangular shape in a plan view and has a size of a short side of 300 to 600 mm × a long side of 1000 to 2000 mm.
【0015】上記断熱材6は、例えば珪酸カルシウムか
らなり、その内側の鋳型面となる全面に黒鉛板7が貼り
付けてある。尚、黒鉛板7に替えて、その領域まで断熱
材6からなるものにしても良い。この形態では、溶湯M
および鋳塊Cに接する部分に固体潤滑剤(例えば、炭素
粒や窒化ボロン(BN))を塗布しても良い。また、冷却
リング8の中空部9から内側で且つ斜め下向きにスリッ
トsが四角形状に形成され、中空部9に供給した高圧水
Wを、四角錐状の冷却水(冷却液)Wの膜として噴射可能
としている。尚、スリットsに替えて貫通孔にしても良
い。更に、図1に示すように、スパウト10の下端付近
には、水平な分流板12が配置され、且つスパウト10
の下方の外側には、一定の間隔を置いてアルミニウムの
溶湯M上に浮上するリング形のフロート14が配置され
る。The heat insulating material 6 is made of, for example, calcium silicate, and a graphite plate 7 is adhered to the entire inner surface of the heat insulating material, which is a mold surface. The graphite plate 7 may be replaced with the heat insulating material 6 up to that region. In this form, molten metal M
Also, a solid lubricant (for example, carbon particles or boron nitride (BN)) may be applied to the portion in contact with the ingot C. Further, the slits s are formed in a square shape inwardly and obliquely downward from the hollow portion 9 of the cooling ring 8, and the high pressure water W supplied to the hollow portion 9 is used as a film of the cooling water (cooling liquid) W in the shape of a quadrangular pyramid. It is possible to inject. Incidentally, a through hole may be used instead of the slit s. Further, as shown in FIG. 1, a horizontal flow dividing plate 12 is arranged near the lower end of the spout 10 and
A ring-shaped float 14 that floats on the molten metal M of aluminum is arranged outside the lower part of the float at regular intervals.
【0016】次に、上記鋳造装置1を用いて、本発明の
連続鋳造方法について説明する。予め、水平鋳型2の内
側の中空部5の下部には、下型16が挿入されている。
係る状態で、図1に示すように、予め不純物を除去して
精製した純アルミニウムの溶湯Mを、スパウト10中で
注下させ且つ分流板12に衝突させて、図1上方の矢印
のように、溶湯Mを水平鋳型2の内側の中空部5内に放
射状に供給する。係る中空部5内で且つ下型16の上に
順次供給された溶湯Mは、黒鉛板7に接触した後で冷却
リング8の内側表面により接触して冷却され、更に冷却
リング8から噴射される冷却水Wにより、強制的に冷却
されるため、その外側面から凝固し始める。係る凝固に
より、図1に示すように、固相線Kの下方に鋳塊Cが順
次形成される。固相線Kは、水冷鋳型2に接する最外寄
りで最も高く、次いで冷却水Wにより冷却されて中心部
寄りに延びるため、中心部付近が最も低くなる。Next, the continuous casting method of the present invention using the casting apparatus 1 will be described. The lower mold 16 is previously inserted in the lower portion of the hollow portion 5 inside the horizontal mold 2.
In such a state, as shown in FIG. 1, pure aluminum molten metal M, which has been purified by removing impurities in advance, is poured into the spout 10 and collided with the flow dividing plate 12, and as shown by an arrow in the upper part of FIG. , The molten metal M is radially supplied into the hollow portion 5 inside the horizontal mold 2. The molten metal M sequentially supplied in the hollow portion 5 and above the lower mold 16 is contacted with the graphite plate 7 and then contacted by the inner surface of the cooling ring 8 to be cooled, and further injected from the cooling ring 8. Since it is forcibly cooled by the cooling water W, it begins to solidify from its outer surface. By such solidification, as shown in FIG. 1, ingots C are sequentially formed below the solidus line K. The solidus line K is highest at the outermost portion in contact with the water-cooled mold 2, and then is cooled by the cooling water W and extends toward the central portion. Therefore, the solidus line K is lowest near the central portion.
【0017】また、図1に示すように、溶湯Mが冷却さ
れる冷却リング8の上端から冷却水Wの噴射位置までの
距離Lが、鋳型装置1における有効モールド長となる。
尚、係る有効モールド長Lは、断熱材6を用いたシェル
フリー鋳造法の鋳造装置1では、通常の金属製冷却鋳型
を用いる連続鋳造法よりも、一般的に短くなる。更に、
冷却リング8の鋳型長さ(図1での垂直方向の長さ)を短
くし、鋳造速度を低め、あるいは冷却水Wの給水量を増
加させるの少なくとも何れか1つの調整を行うことによ
り、溶湯Mからこれが凝固した本発明のアルミニウム鋳
塊Cに変化する凝固開始点Gを、図1に示すように、耐
火性断熱材6の領域内で生じさせることができる。Further, as shown in FIG. 1, the distance L from the upper end of the cooling ring 8 for cooling the molten metal M to the injection position of the cooling water W is the effective mold length in the mold apparatus 1.
In addition, the effective mold length L is generally shorter in the casting apparatus 1 of the shell-free casting method using the heat insulating material 6 than in the continuous casting method using a normal metal cooling mold. Furthermore,
By adjusting at least one of shortening the mold length of the cooling ring 8 (length in the vertical direction in FIG. 1), lowering the casting speed, or increasing the amount of cooling water W supplied, A solidification starting point G, which changes from M to the solidified aluminum ingot C of the present invention, can be generated in the region of the refractory heat insulating material 6 as shown in FIG.
【0018】以上のように、黒鉛板7を内貼りした上記
断熱材6を水冷鋳型2の上端部3寄りに配置し、有効モ
ールド長Lを比較的短くし、且つ凝固開始点Gを上記断
熱材6の領域内にすることにより、溶湯Mからの抜熱を
冷却水Wが噴射される下向き方向に集中させることがで
きる。この結果、アルミニウム鋳塊Cは、その表面に近
い固相線K付近における核生成が抑制されると共に、生
成される[100]軸の向きが鋳造方向(図1で垂直方
向)とほぼ平行な柱状晶の成長を維持することができ
る。また、図1に示すように、固相線Kは鋳塊Cの中心
部に向かうに連れて低くなるが、鋳塊Cの柱状晶は係る
固相線に対し垂直に成長するため、係る柱状晶の形状は
鋳塊Cの内部に沿ったものとなる。但し、この場合で
も、上記[100]軸と鋳造方向との関係は維持され
る。従って、ほとんどの柱状晶は、鋳造方向にほぼ沿っ
た[100]軸を持った柱状晶に制御されている。As described above, the heat insulating material 6 having the graphite plate 7 adhered therein is arranged near the upper end 3 of the water-cooled mold 2 so that the effective mold length L is relatively short and the solidification starting point G is the heat insulating material. By setting it within the region of the material 6, the heat removal from the molten metal M can be concentrated in the downward direction in which the cooling water W is jetted. As a result, in the aluminum ingot C, nucleation is suppressed in the vicinity of the solidus line K close to the surface of the ingot C, and the direction of the [100] axis is almost parallel to the casting direction (vertical direction in FIG. 1). The growth of columnar crystals can be maintained. Further, as shown in FIG. 1, the solidus line K becomes lower toward the center of the ingot C, but since the columnar crystals of the ingot C grow perpendicularly to the solidus line, The crystal shape follows the inside of the ingot C. However, even in this case, the relationship between the [100] axis and the casting direction is maintained. Therefore, most of the columnar crystals are controlled to have columnar crystals having a [100] axis substantially along the casting direction.
【0019】この結果、固相線Kの下方で凝固し且つ図
1下方の太い矢印に沿って下型16と共に順次下降する
鋳塊Cのうち定常条件で凝固した全領域で、図1に示す
ように、鋳造方向とほぼ平行(図1の垂直線に対し±1
5度以下も含む)な[100]軸zを持った柱状晶Sを
形成することが可能となる。尚、下型16は、アルミニ
ウム鋳塊Cの垂直方向への伸長に応じて、図示しないピ
ット内に下降し、鋳込み方向の長さが例えば4〜6メー
トルとなった時点で停止する。また、以上のようなアル
ミニウム鋳塊Cは、電磁鋳造法やOCCプロセスによっ
ても、溶湯Mからの抜熱を鋳造方向に集中させることに
より、連続鋳造することができる。As a result, FIG. 1 shows the entire region of the ingot C which solidifies below the solidus line K and descends with the lower mold 16 along the thick arrow at the bottom of FIG. Is almost parallel to the casting direction (± 1 against the vertical line in Fig. 1).
It is possible to form columnar crystals S having a [100] axis z of 5 degrees or less). The lower mold 16 descends into a pit (not shown) in accordance with the vertical expansion of the aluminum ingot C, and stops when the length in the casting direction reaches, for example, 4 to 6 meters. Further, the aluminum ingot C as described above can be continuously cast also by the electromagnetic casting method or the OCC process by concentrating the heat removal from the molten metal M in the casting direction.
【0020】上述した[100]軸zを有する柱状晶S
を全領域で有する鋳塊Cを用いた電解コンデンサの電極
用アルミニウム箔の製造方法を、図2(A)により説明す
る。前述した連続鋳造工程S1で得られた上記アルミニ
ウム鋳塊Cについて、不要な周辺部を面削した後、図示
しない均熱炉に装入し、図2(A)に示すように、約40
0〜620℃に加熱し且つ例えば48時間にわたり保持
する均質化処理S2を先ず行う。尚、上記面削は、係る
均質化処理S2の後で行っても良い。次に、図2(A)に
示すように、上記温度域のアルミニウム鋳塊Cを圧延機
に通す熱間圧延S3(成形工程)を行う。熱間圧延S3に
は、例えばタンデム式4段圧延機などが用いられ、前記
鋳造方向に沿った圧延方向とし、任意の圧化率で且つ任
意数のパスを行って、厚みが約7mmの図示しないコイ
ルに成形する。The columnar crystal S having the above-mentioned [100] axis z
A method of manufacturing an aluminum foil for an electrode of an electrolytic capacitor using a cast ingot C having the entire region will be described with reference to FIG. The aluminum ingot C obtained in the above-mentioned continuous casting step S1 is chamfered at an unnecessary peripheral portion and then charged into a soaking furnace (not shown), and as shown in FIG.
First, a homogenization treatment S2 of heating to 0 to 620 ° C. and holding for 48 hours is performed. The chamfering may be performed after the homogenizing process S2. Next, as shown in FIG. 2 (A), hot rolling S3 (forming step) of passing the aluminum ingot C in the above temperature range through a rolling mill is performed. For the hot rolling S3, for example, a tandem type four-high rolling mill is used, and the rolling direction is along the casting direction, the compression ratio is arbitrary, and an arbitrary number of passes are performed to show a thickness of about 7 mm. Do not shape into a coil.
【0021】次いで、熱間圧延S3により得られたコイ
ルを室温に冷却した後、図2(A)に示すように、冷間圧
延(成形工程)S4を行う。係る冷間圧延S4には、例え
ば2タンデム4段圧延機やシングル4段圧延機などが用
いられ、前記鋳造方向に沿った圧延方向とし、圧下率が
約30〜70%で5〜10パスを行うことにより、厚み
が約130μmの図示しないアルミニウム箔に成形す
る。最後に、300〜600℃に加熱し且つ例えば24
時間にわたり保持する仕上げ焼鈍(熱処理工程)S7を行
う。この結果、前記圧延S3,S4により圧延方向に沿
って変形した歪みを含む加工組織を、歪みのない立方体
方位の結晶粒に再結晶させたアルミニウム箔とすること
ができる。Next, after cooling the coil obtained by the hot rolling S3 to room temperature, as shown in FIG. 2 (A), cold rolling (forming step) S4 is performed. For the cold rolling S4, for example, a 2-tandem 4-high rolling mill or a single 4-high rolling mill is used, and the rolling direction is along the casting direction, and the rolling reduction is about 30 to 70% and 5 to 10 passes are performed. By doing so, an aluminum foil (not shown) having a thickness of about 130 μm is formed. Finally, heat to 300-600 ° C. and for example 24
A finish annealing (heat treatment step) S7 of holding for a time is performed. As a result, it is possible to obtain an aluminum foil in which the processed structure including the strain deformed along the rolling direction by the rolling S3 and S4 is recrystallized into crystal grains having a cubic orientation and having no strain.
【0022】尚、図2(B)に示すように、冷間圧延S4
後のアルミニウム箔に対し、中間焼鈍S5を施しても良
い。係る焼鈍S5は、180〜300℃に加熱し例えば
12時間保持した後、室温に冷却するもので、次述する
仕上げ冷間圧延S6や仕上げ焼鈍S7と組み合わせて、
前記圧延S3,S4により圧延方向に沿って変形した歪
みを含む加工組織から歪みのない立方体方位結晶を鮮鋭
化することができる。引き続いて、図2(B)に示すよう
に、仕上げ冷間圧延S6を、極く低い圧下率で1パスに
て行うことにより、約110μmの厚みとしたアルミニ
ウム箔に整形する。そして、前述した仕上げ焼鈍S7を
行うことにより、立方体方位が鮮鋭化した上記アルミニ
ウム箔を一層確実に得ることができる。As shown in FIG. 2B, cold rolling S4
The subsequent aluminum foil may be subjected to intermediate annealing S5. Such annealing S5 is to heat to 180 to 300 ° C., hold for, for example, 12 hours, and then cool to room temperature. In combination with finish cold rolling S6 and finish annealing S7 described below,
By the rolling S3 and S4, a strain-free cubic oriented crystal can be sharpened from a processed structure including a strain deformed along the rolling direction. Subsequently, as shown in FIG. 2 (B), finish cold rolling S6 is performed in one pass at an extremely low reduction ratio to shape an aluminum foil having a thickness of about 110 μm. Then, by performing the above-mentioned finish annealing S7, it is possible to more reliably obtain the above-mentioned aluminum foil having a sharpened cubic orientation.
【0023】[0023]
【実施例】以下において、本発明の具体的な実施例を説
明する。表1に示す組成の純アルミニウムの溶湯Mを、
前記図1に示した鋳造装置1を用いて個別に連続鋳造す
ることにより、厚さ508mm×幅1080mmの実施
例1〜4のアルミニウム鋳塊Cを得た。これらの連続鋳
造における有効モールド長L、冷却水量、鋳造温度、お
よび下型16の下降速度も表1に示した。一方、表1に
示す純アルミニウムの溶湯Mを、表1に示す有効モール
ド長L、冷却水量、鋳造温度、および下型の下降速度で
連続鋳造することにより、同様の寸法の比較例のアルミ
ニウム鋳塊Cを得た。係る比較例の有効モールド長L
が、実施例1〜4のそれよりも長いのは、比較例に用い
る水冷鋳型が、前述した従来の連続鋳造法に用いるもの
と同様の全体が金属製で且つ内部に冷却水が充填された
形態であることに起因する。EXAMPLES Specific examples of the present invention will be described below. The molten aluminum M having the composition shown in Table 1 is
By continuously casting individually using the casting apparatus 1 shown in FIG. 1, aluminum ingots C of Examples 1 to 4 having a thickness of 508 mm and a width of 1080 mm were obtained. Table 1 also shows the effective mold length L, the amount of cooling water, the casting temperature, and the lowering speed of the lower mold 16 in these continuous castings. On the other hand, by continuously casting the molten metal M of pure aluminum shown in Table 1 at the effective mold length L, the cooling water amount, the casting temperature, and the lowering speed of the lower die shown in Table 1, the aluminum casting of the comparative example of the same size was performed. Mass C was obtained. Effective mold length L of the comparative example
However, what is longer than that of Examples 1 to 4 is that the water-cooled mold used in the comparative example is entirely made of metal similar to that used in the conventional continuous casting method described above, and the inside thereof is filled with cooling water. Due to the form.
【0024】[0024]
【表1】 [Table 1]
【0025】実施例2のアルミニウム鋳塊Cを鋳造方向
と直角に切断し、露出した切断面を、塩酸:硝酸:弗酸
を50:50:1の割合に調整した薬品(腐食液)で溶解
し、垂直でない光を用いて写真撮影した。その結果、図
3(A)に示すように、幅方向のエッジ部(縁部)からセン
ター付近にわたって、黒色に映る[100]柱状晶が比
較的多く発達し、且つ白色に映る非[100]柱状晶の
発達が著しく抑制されていたことが判明した。尚、実施
例1,3,4の鋳塊Cも上記と同様であった。一方、比
較例のアルミニウム鋳塊Cについても、上記同様に切
断、処理、および写真撮影した結果、前記図4(B)と同
様に、幅方向のエッジ(縁部)寄りでは、白色に映る非
[100]柱状晶が比較的多く発達し、幅方向のセンタ
ー寄りでは黒色に映る[100]柱状晶が比較的多く発
達していた。以上の結果、本発明のアルミニウム鋳塊C
およびその連続鋳造方法の効果が裏付けられた。The aluminum ingot C of Example 2 was cut at a right angle to the casting direction, and the exposed cut surface was dissolved with a chemical (corrosion solution) adjusted to a ratio of hydrochloric acid: nitric acid: hydrofluoric acid of 50: 50: 1. However, it was photographed using non-vertical light. As a result, as shown in FIG. 3 (A), from the edge portion (edge portion) in the width direction to the vicinity of the center, a relatively large amount of [100] columnar crystals appearing in black develop and non- [100] appearing in white. It was found that the growth of columnar crystals was significantly suppressed. The ingot C of Examples 1, 3 and 4 was the same as above. On the other hand, the aluminum ingot C of the comparative example was also cut, treated, and photographed in the same manner as described above, and as a result, similar to FIG. 4B, a non-white image was observed near the edge in the width direction. A relatively large amount of [100] columnar crystals were developed, and a relatively large amount of [100] columnar crystals, which appeared black in the center of the width direction, were developed. As a result of the above, the aluminum ingot C of the present invention
And the effect of the continuous casting method was confirmed.
【0026】また、実施例2および比較例のアルミニウ
ム鋳塊Cを前述した熱間圧延S3および冷間圧延S4に
より厚さ130μmのアルミニウム箔とすると共に、2
60℃で5時間加熱する中間焼鈍S5および仕上げ冷間
圧延S6で厚さ110μmのアルミニウム箔とした。こ
れらについて、500℃で1時間加熱する仕上げ焼鈍S
7を施した。得られた実施例2および比較例のアルミニ
ウム箔に対し、上記同様の薬品で溶解して露出した表面
を、上記同様に写真撮影した。その結果、実施例2のア
ルミニウム箔では、図3(B)に示すように、幅方向のエ
ッジ部からセンター付近にわたり、黒色に映る立方体方
位の結晶粒が比較的多く発達し、且つ白色に映る非立方
体方位の結晶粒の発達が著しく抑制されていた。尚、実
施例1,3,4のアルミニウム箔も上記と同様であっ
た。Further, the aluminum ingots C of Example 2 and Comparative Example were made into an aluminum foil having a thickness of 130 μm by the above-mentioned hot rolling S3 and cold rolling S4, and 2
An aluminum foil having a thickness of 110 μm was obtained by intermediate annealing S5 heating at 60 ° C. for 5 hours and finish cold rolling S6. About these, finish annealing S which is heated at 500 ° C for 1 hour
7 was applied. The surfaces of the obtained aluminum foils of Example 2 and Comparative Example, which had been exposed by melting with the same chemicals as above, were photographed in the same manner as above. As a result, in the aluminum foil of Example 2, as shown in FIG. 3 (B), from the edge portion in the width direction to the vicinity of the center, a relatively large number of cubic-oriented crystal grains appearing in black developed and appeared in white. The development of grains with non-cubic orientation was significantly suppressed. The aluminum foils of Examples 1, 3 and 4 were the same as above.
【0027】一方、比較例のアルミニウム箔では、前記
図4(A)と同様に、幅方向のエッジ付近で白色に映る非
立方体方位の結晶粒が発達していた。以上の結果から、
本発明の製造方法により得られた実施例のアルミニウム
箔では、コイルの全領域で立方体方位の結晶粒が鮮鋭
(顕在)化していた。即ち、上記箔中において、立方体方
位の結晶粒が全領域で均一に分布しており、これにより
電解コンデンサの電極として用いた場合でも、所要の特
性(例えば静電容量)を安定して発揮し且つ信頼性を高め
られることが判明した。係る実施例によって、本発明に
よる電解コンデンサの電極用アルミニウム箔の製造方法
の効果が裏付けられた。On the other hand, in the aluminum foil of the comparative example, as in the case of FIG. 4 (A), non-cubic crystal grains which appear white in the vicinity of the edges in the width direction were developed. From the above results,
In the aluminum foil of the example obtained by the manufacturing method of the present invention, the crystal grains in the cubic orientation were sharp in the entire region of the coil.
It was (realized). That is, in the foil, the crystal grains in the cubic orientation are uniformly distributed in the entire region, and thus even when used as the electrode of the electrolytic capacitor, the required characteristics (e.g. capacitance) are stably exhibited. It has also been found that the reliability can be increased. Such an example supports the effect of the method for producing an aluminum foil for an electrode of an electrolytic capacitor according to the present invention.
【0028】[0028]
【発明の効果】以上に説明した本発明におけるアルミニ
ウム鋳塊(請求項1)によれば、前記冷却鋳型に供給され
たアルミニウムの溶湯は係る鋳型により冷却されつつ凝
固し始め、定常部で鋳型からの抜熱が抑制され、鋳造初
期の凝固時に核生成した結晶のうち、鋳造方向にほぼ平
行な[100]軸を有する結晶のみが優先的に成長して
いる。この結果、ほとんどの柱状晶はその[100]軸
が鋳造方向とほぼ平行になっている。また、水冷鋳型の
下端部から順次引き下ろした鋳塊に冷却液を注加されて
いるため、鋳造方向に沿ってほぼ平行な[100]軸を
有する柱状晶が全体に形成されたアルミニウム鋳塊とな
る。According to the aluminum ingot (Claim 1) of the present invention described above, the molten aluminum supplied to the cooling mold begins to solidify while being cooled by the mold, and the molten aluminum flows from the mold at the stationary portion. Heat removal is suppressed, and among crystals nucleated during solidification in the initial stage of casting, only crystals having a [100] axis substantially parallel to the casting direction grow preferentially. As a result, the [100] axis of most columnar crystals is almost parallel to the casting direction. In addition, since the cooling liquid is poured into the ingots sequentially drawn from the lower end of the water-cooled mold, the aluminum ingots having columnar crystals having [100] axes substantially parallel to each other along the casting direction are formed. Become.
【0029】また、請求項2のアルミニウムの連続鋳造
方法によれば、冷却鋳型の溶湯注入側を耐火性断熱材に
より構成しているため、溶湯から上記鋳型を介する抜熱
が抑制される。この結果、溶湯からの抜熱は、冷却液に
より冷却される下方にのみ向かい、鋳造方向に沿った
[100]軸を有する柱状晶が鋳塊の全体で生成され
る。しかも、冷却鋳型における冷却リングの鋳型長さ、
鋳造速度、冷却液量の何れかを調整して、溶湯の凝固開
始点を耐火性断熱材の領域内にするため、冷却鋳型から
の抜熱を抑制し且つ下方への上記抜熱のみに制限し易く
なる。この結果、鋳造の定常部において、非[100]
柱状晶の核生成が抑制され、且つほぼ鋳造方向に沿った
[100]軸を有する柱状晶が全体に形成された鋳塊を
一層確実に得ることができる。更に、請求項3のアルミ
ニウムの連続鋳造方法によれば、黒鉛などからなる鋳型
面を有する鋳型面がアルミニウムの溶湯に接触するた
め、断熱材の劣化を防止し且つ上記鋳型を介する抜熱を
一層抑制することができる。しかも、上記鋳型面のレベ
ル中において、溶湯の凝固開始点が生じるため、表面近
傍の新たな核生成を抑制し、鋳造方向に平行な[10
0]軸を有する下方からの柱状晶の成長が維持できる。
従って、[100]軸が鋳造方向にほぼ平行な柱状晶を
全体に形成したアルミニウム鋳塊を容易に製造すること
ができる。Further, according to the aluminum continuous casting method of the second aspect, since the molten metal injection side of the cooling mold is made of a refractory heat insulating material, heat removal from the molten metal through the mold is suppressed. As a result, the heat removal from the molten metal is directed only to the lower side where it is cooled by the cooling liquid, and columnar crystals having the [100] axis along the casting direction are generated in the entire ingot. Moreover, the mold length of the cooling ring in the cooling mold,
Adjusting either the casting speed or the amount of cooling liquid so that the solidification start point of the molten metal is within the area of the refractory heat insulating material, so that heat removal from the cooling mold is suppressed and only the above heat removal downward is limited. Easier to do. As a result, in the steady part of casting, non- [100]
It is possible to more reliably obtain an ingot in which the nucleation of the columnar crystals is suppressed and the columnar crystals having the [100] axis substantially along the casting direction are entirely formed. Further, according to the continuous casting method for aluminum of claim 3, since the mold surface having a mold surface made of graphite or the like comes into contact with the molten aluminum, deterioration of the heat insulating material is prevented and heat removal through the mold is further improved. Can be suppressed. Moreover, since a solidification start point of the molten metal occurs in the level of the mold surface, new nucleation near the surface is suppressed, and [10]
The growth of columnar crystals from below having the [0] axis can be maintained.
Therefore, it is possible to easily manufacture an aluminum ingot having columnar crystals whose [100] axis is substantially parallel to the casting direction.
【0030】一方、本発明における電解コンデンサの電
極用アルミニウム箔の製造方法(請求項4)によれば、前
記鋳塊に対して、鋳造方向に沿った圧延方向(長手方向)
の熱間圧延および冷間圧延などの成形工程および仕上げ
焼鈍などの熱処理工程が施される。従って、全領域で立
方体方位の結晶粒が鮮鋭(顕在)化し、例えば静電容量な
どの特性が優れた電解コンデンサの電極用アルミニウム
箔を確実に製造することができる。また、請求項5の電
解コンデンサの電極用アルミニウム箔の製造方法によれ
ば、更に鮮鋭(顕在)化された立方体方位の結晶粒を有す
るアルミニウム箔を一層確実に製造することができる。On the other hand, according to the method for producing an aluminum foil for an electrode of an electrolytic capacitor according to the present invention (claim 4), the rolling direction (longitudinal direction) along the casting direction is applied to the ingot.
Forming steps such as hot rolling and cold rolling and heat treatment steps such as finish annealing are performed. Therefore, the crystal grains in the cubic orientation are sharpened (revealed) in the entire region, and the aluminum foil for electrodes of the electrolytic capacitor having excellent characteristics such as capacitance can be reliably manufactured. Further, according to the method for producing an aluminum foil for an electrode of an electrolytic capacitor of the fifth aspect, it is possible to more reliably produce an aluminum foil having crystal grains in a cubic orientation which are further sharpened.
【図1】本発明の連続鋳造方法を示す概略図。FIG. 1 is a schematic view showing a continuous casting method of the present invention.
【図2】(A),(B)は本発明の電極用アルミニウム箔の
製造方法を示す流れ図。2A and 2B are flow charts showing a method for manufacturing an aluminum foil for electrodes of the present invention.
【図3】(A),(B)は実施例の鋳塊またはアルミニウム
箔の組織を示す模式的図面。3 (A) and 3 (B) are schematic drawings showing a structure of an ingot or an aluminum foil of an example.
【図4】(A),(B)は従来のアルミニウム箔または鋳塊
の組織を示す模式的図面。4A and 4B are schematic drawings showing the structure of a conventional aluminum foil or ingot.
2……水冷鋳型(冷却鋳型), 3……上端部,4
……下端部, 6……耐火性断熱
材,7……黒鉛板(鋳型面), 8……冷却リ
ング,M……溶湯, C……アル
ミニウム鋳塊,W……冷却水(冷却液), G
……凝固開始点,S……柱状晶,
z……[100]軸S3…熱間圧延,
S4…冷間圧延,S5…中間焼鈍,
S6…仕上げ冷間圧延,S7…仕上げ焼鈍2 ... Water-cooled mold (cooling mold), 3 ... Upper end, 4
...... Lower end part, 6 ... Fireproof heat insulating material, 7 ... Graphite plate (mold surface), 8 ... Cooling ring, M ... Molten metal, C ... Aluminum ingot, W ... Cooling water (cooling liquid) , G
…… Solidification starting point, S …… Columnar crystal,
z ... [100] axis S3 ... hot rolling,
S4 ... Cold rolling, S5 ... Intermediate annealing,
S6 ... Finish cold rolling, S7 ... Finish annealing
フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) B22D 11/059 B22D 11/059 110 110F 120 120A (72)発明者 石渡 保生 静岡県庵原郡蒲原町蒲原161番地 日本軽 金属株式会社蒲原電解・鋳造工場内 (72)発明者 名和田 進 静岡県庵原郡蒲原町蒲原1丁目34番1号 日本軽金属株式会社グループ技術センター 内 (72)発明者 東野 和美 静岡県庵原郡蒲原町蒲原161番地 日本軽 金属株式会社蒲原製造所内 (72)発明者 土屋 清美 静岡県庵原郡蒲原町蒲原1丁目34番1号 株式会社日軽分析センター内 Fターム(参考) 4E002 AA08 AD13 BD02 BD09 4E004 AA07 NA02 NC08 Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B22D 11/059 B22D 11/059 110 110F 120 120A (72) Inventor Yasushi Ishiwata 161, Kambara, Kambara-cho, Anbara-gun, Shizuoka Metal Co., Ltd. in Kambara Electrolysis and Casting Factory (72) Inventor Susumu Nawada 1-34-1 Kambara, Kambara-cho, Anbara-gun, Shizuoka Prefecture Nippon Light Metal Co., Ltd. Group Technology Center (72) Inventor Kazumi Higashino Kambara, Anbara-gun, Shizuoka Prefecture 161, Machi Kambara Nippon Light Metal Co., Ltd., Kambara Works (72) Inventor Kiyomi Tsuchiya 1-34-1 Kambara, Kambara-cho, Anbara-gun, Shizuoka Prefecture F-term (reference) 4E002 AA08 AD13 BD02 BD09 4E004 AA07 NA02 NC08
Claims (5)
鋳型の上端部からアルミニウムの溶湯を供給しつつ冷却
して凝固した鋳塊を下端部から引き下ろし且つ冷却液を
注加して連続鋳造されるアルミニウム鋳塊であって、 鋳造初期に核生成した結晶が柱状晶として上方および内
部方向にほぼ沿って成長し且つ定常部の鋳塊の表面から
の新たな結晶の核生成が生じていないと共に、上記鋳塊
における柱状晶の[100]軸が鋳造方向とほぼ平行で
ある、 ことを特徴とするアルミニウム鋳塊。1. An ingot, which is solidified by cooling while supplying a molten aluminum from an upper end of a cylindrical cooling mold whose upper end and lower end are open, is drawn down from the lower end and a cooling liquid is added to continue. In an aluminum ingot to be cast, nucleated crystals at the initial stage of casting grow as columnar crystals substantially along the upper and inner directions, and new crystals nucleate from the surface of the ingot in the steady part. In addition, the aluminum ingot is characterized in that the [100] axis of the columnar crystal in the ingot is substantially parallel to the casting direction.
鋳型の上端部からアルミニウムの溶湯を供給すると共
に、冷却して凝固した鋳塊を下端部から引き下ろし且つ
冷却液を注加してアルミニウム鋳塊を連続鋳造する方法
において、 上記冷却鋳型の上端部における上記溶湯注入側が、耐火
性断熱材からなると共に、上記冷却鋳型における冷却リ
ングの鋳型長さ、鋳造速度、および冷却液量の少なくと
も1つ以上を調整することにより、上記アルミニウムの
溶湯の凝固開始点が上記耐火性断熱材の領域内で生じ
る、 ことを特徴とするアルミニウム鋳塊の連続鋳造方法。2. A molten aluminum is supplied from the upper end of a cylindrical cooling mold having an open upper end and a lower end, and a cooled and solidified ingot is drawn down from the lower end and a cooling liquid is added. In the method of continuously casting an aluminum ingot, the molten metal injection side at the upper end of the cooling mold is made of a refractory heat insulating material, and the mold length of the cooling ring in the cooling mold, the casting speed, and at least the cooling liquid amount. A continuous casting method of an aluminum ingot, wherein the solidification start point of the molten aluminum is generated in the region of the refractory heat insulating material by adjusting one or more.
の耐火性断熱材の内側に、黒鉛またはこれと同等の特性
を有する鋳型面を形成すると共に、前記アルミニウムの
溶湯の凝固開始点が上記鋳型面において生じる、 ことを特徴とする請求項2に記載のアルミニウム鋳塊の
連続鋳造方法。3. A mold surface having the same characteristics as graphite is formed inside the refractory heat insulating material on the molten metal injection side at the upper end of the cooling mold, and the solidification starting point of the molten aluminum is the above. It occurs on the mold surface. The continuous casting method for an aluminum ingot according to claim 2, characterized in that.
処理し、 その後、係る鋳塊の上記鋳造時の鋳造方向を圧延方向と
する熱間圧延と冷間圧延とを含む成形工程および仕上げ
焼鈍を含む熱処理工程を施す、 ことを特徴とする電解コンデンサの電極用アルミニウム
箔の製造方法。4. A forming step and a finish including homogenizing the aluminum ingot according to claim 1, and thereafter including hot rolling and cold rolling in which a rolling direction is a casting direction during the casting of the ingot. A method of manufacturing an aluminum foil for an electrode of an electrolytic capacitor, which comprises performing a heat treatment step including annealing.
の間において、中間焼鈍および仕上げ冷間圧延を更に施
される、ことを特徴とする請求項4に記載の電解コンデ
ンサの電極用アルミニウム箔の製造方法。5. The electrode of the electrolytic capacitor according to claim 4, wherein the ingot is further subjected to intermediate annealing and finish cold rolling between the cold rolling and the finish annealing. For manufacturing aluminum foil for automobiles.
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