JP2540110B2 - Electro aluminum plating method - Google Patents
Electro aluminum plating methodInfo
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- JP2540110B2 JP2540110B2 JP62174522A JP17452287A JP2540110B2 JP 2540110 B2 JP2540110 B2 JP 2540110B2 JP 62174522 A JP62174522 A JP 62174522A JP 17452287 A JP17452287 A JP 17452287A JP 2540110 B2 JP2540110 B2 JP 2540110B2
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- aluminum
- plating
- bath
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- halide
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、溶融塩浴による電気アルミニウムめっき方
法に関する。TECHNICAL FIELD The present invention relates to a method for electroplating aluminum with a molten salt bath.
（従来技術） アルミニウムの電気めっきは、アルミニウムの酸素に
対する親和力が大きく、電位が水素より卑であるので、
水溶液系のめっき浴で行うことが困難である。このた
め、従来よりアルミニウムの電気めっきは、非水溶液系
めっき浴、特に有機溶媒系のめっき浴で行なわれてい
る。(Prior art) Aluminum electroplating has a high affinity for aluminum for oxygen and a potential lower than that of hydrogen.
It is difficult to perform in an aqueous plating bath. Therefore, aluminum electroplating has been conventionally performed in a non-aqueous solution type plating bath, particularly in an organic solvent type plating bath.
この有機溶媒系のめっき浴としては、AlCl3とLiAlH4
またはLiHとをエーテルに溶解したものやAlCl3とLiAlH4
とをTHF（テトラヒドロフラン）に溶解したもの、ある
いは西ドイツのシーメンス・リサーチ・ラボラトリーに
より1975年に工業化の検討が進められ、1980年にオラン
ダのベギン・ガルバノ・アルミニウムによって工業用パ
イロットプラントが完成したトリエチルアルミニウムを
使用するSIGAL PROCESSなどがある。これらのめっき浴
によれば、純度、加工性および外観の優れたアルミニウ
ムめっきを行なうことができるとされている。This organic solvent-based plating bath includes AlCl 3 and LiAlH 4
Alternatively, LiH dissolved in ether, or AlCl 3 and LiAlH 4
Triethylaluminum in which and were dissolved in THF (tetrahydrofuran), or industrialization was studied in 1975 by Siemens Research Laboratory in West Germany, and an industrial pilot plant was completed by Begin Galvano Aluminum in the Netherlands in 1980. There is a SIGAL PROCESS etc. It is said that these plating baths can perform aluminum plating excellent in purity, workability and appearance.
しかし、これらのめっき浴は、いずれも浴中に非常に
活性なLiAlH4、LiHまたはトリエチルアルミニウムを含
んでいるため、酸素や水分が存在すると、それらと反応
して分解し、電流効率が低下し、浴寿命も短くなってし
まうものであった。また、誤って酸素や水分が多量に混
入すると、爆発の危険性もあった。However, these plating baths all contain very active LiAlH 4 , LiH or triethylaluminum in the baths, so if oxygen or moisture is present, they react with them and decompose, reducing the current efficiency. In addition, the bath life was shortened. There is also a risk of explosion if a large amount of oxygen or water is accidentally mixed.
そこで、このような問題のないめっき浴として、アル
ミニウムハロゲン化物とアルキルピリジニウムハロゲン
化物の溶融塩浴を開発した。Therefore, a molten salt bath of an aluminum halide and an alkylpyridinium halide was developed as a plating bath without such a problem.
このめっき浴は、アルミニウムハロゲン化物（AlX3、
但し、ＸはCl、Br、Ｉ）50〜80モル％とアルキルピリジ
ニウムハロゲン化物（C5H5N−RX、但し、Ｒは炭素数１
〜５のアルキル基、Ｘはハロゲン原子）20〜50モル％と
を溶融したもの、またはこの浴に有機溶剤（好ましくは
芳香族溶剤）を配合したもので、常温付近で液体とな
り、イオン解離する。This plating bath is made of aluminum halide (AlX 3 ,
However, X is Cl, Br, I) 50 to 80 mol% and an alkylpyridinium halide (C 5 H 5 N-RX, where R is a carbon number 1).
~ 5 alkyl group, X is a halogen atom) 20 to 50 mol% melted, or an organic solvent (preferably an aromatic solvent) mixed in this bath, which becomes liquid at around room temperature and ion dissociates .
（発明が解決しようとする問題点） しかし、このめっき浴は、純度の高いアルミニウムハ
ロゲン化物を使用しても、Fe、Pb、H2O等の不純物を含
有するため、不可避的にこれらの不純物が含有され、9
9.9％以上の高純度Alめっきが得られず、しかも浴温を4
0℃以上にすると、不純物の影響が大きく現れて、緻密
なめっきを得ることが困難であった。また、高電流密度
域でめっきすると、めっき層組織が粉末状デンドライト
になってしまうものであった。(Problems to be solved by the invention) However, even if a high-purity aluminum halide is used, this plating bath inevitably contains impurities such as Fe, Pb, and H 2 O. Contains, 9
High-purity Al plating of 9.9% or more was not obtained, and the bath temperature was 4
If the temperature is higher than 0 ° C., the influence of impurities becomes large and it is difficult to obtain a dense plating. Further, when plating is performed in the high current density region, the structure of the plating layer becomes powdery dendrite.
このため、前記めっき浴でめっきしたものは、アルミ
ニウム線との良好なボンディング性を必要とするICリー
ドフレームなどのような電子部品、アルマイト処理によ
るポアーを利用する磁気ディスクなどのような精密製品
に使用するには、まだ問題があった。For this reason, those plated with the plating bath described above are suitable for electronic parts such as IC lead frames that require good bonding properties with aluminum wires, and precision products such as magnetic disks that use pores by anodizing. Still had problems to use.
そこで、これらの用途に適したアルミニウムめっきが
得られるようにするには、めっき浴の純度を高めてめっ
きすることが必要であったが、まだ精製方法は、確立さ
れていなかった。Therefore, in order to obtain aluminum plating suitable for these applications, it was necessary to increase the purity of the plating bath for plating, but the purification method has not been established yet.
（問題点を解決するための手段） 本発明は、アルミニウムハロゲン化物（AlX3、但し、
ＸはCl、Br、Ｉ）50〜80モル％とアルキルピリジニウム
ハロゲン化物（C5H5N−RX、但し、Ｒは炭素数１〜５の
アルキル基、Ｘはハロゲン原子）20〜50モル％とからな
る溶融塩浴またはこの浴に有機溶剤を配合したものを両
極に金属アルミニウムを用いて0.5A/dm2以下の電流密度
で予備電解することにより精製し、その後被めっき物に
アルミニウムを電気めっきすることにより高純度のめっ
きが得られるようにした。そして、この精製により被め
っき物へのめっきの際、乾燥無酸素雰囲気中で直流電流
またはパルス電流により浴温０〜150℃、電流密度0.1〜
30A/dm2まで浴温、電流密度を高くできるようにした。(Means for Solving Problems) The present invention is directed to an aluminum halide (AlX 3 , provided that
X is Cl, Br, I) 50 to 80 mol% and an alkylpyridinium halide (C 5 H 5 N-RX, where R is an alkyl group having 1 to 5 carbon atoms and X is a halogen atom) 20 to 50 mol% A molten salt bath consisting of or and a mixture of this bath and an organic solvent are purified by pre-electrolyzing at a current density of 0.5 A / dm 2 or less using metallic aluminum on both electrodes, and then aluminum is electroplated on the object to be plated. High-purity plating was obtained by plating. And when plating on the object to be plated by this purification, the bath temperature is 0 to 150 ° C and the current density is 0.1 to 10 by a direct current or a pulsed current in a dry oxygen-free atmosphere.
The bath temperature and current density could be increased up to 30 A / dm 2 .
本発明でのめっき浴精製は、Alと不純物のFe、Pb等と
の電位差を利用して、不純物をAl陰極表面に置換析出さ
せ、除去するのであるが、その際、陰極に加わる負の電
圧で不純物の移動を速め、析出を促進させるのである。
電解は不純物の析出が多く、Alの析出の少ない電流密度
である0.5A/dm2以下で行う。この予備電解は、電流密度
0.5A/dm2以下で、通常１時間以上行えば精製することが
できる。電流密度を0.5A/dm2以上にすと、Alの析出が主
となり、不純物析出に対するAl析出が多くなり、Alの浪
費が多くなる。The plating bath refining in the present invention utilizes the potential difference between Al and impurities Fe, Pb, etc. to deposit and remove the impurities on the surface of the Al cathode, and remove the negative voltage applied to the cathode at that time. This accelerates the movement of impurities and promotes precipitation.
The electrolysis is performed at a current density of 0.5 A / dm 2 or less, which is a concentration of impurities and a small amount of Al. This pre-electrolysis is the current density
Purification can be carried out at 0.5 A / dm 2 or less and usually for 1 hour or more. When the current density is set to 0.5 A / dm 2 or more, the precipitation of Al becomes the main, the precipitation of Al against the precipitation of impurities increases, and the waste of Al increases.
なお、この方法で陽極をAlにするのは、陽極を不溶性
極にすると、上記電流密度での予備電解により浴中のAl
が析出した場合のめっき浴組成変動を防止するためであ
る。Al陽極にすれば、通電量に比例して、陽極よりAlが
溶解供給され、めっき浴組成は、建浴時の状態に保たれ
る。In this method, the anode is made of Al because when the anode is made an insoluble electrode, the Al in the bath is preliminarily electrolyzed at the above current density.
This is to prevent fluctuations in the composition of the plating bath when is deposited. If an Al anode is used, Al is dissolved and supplied from the anode in proportion to the amount of electricity supplied, and the plating bath composition is maintained in the state at the time of building the bath.
これらの方法によりめっき浴を精製すると、建浴時の
Fe分0.01〜0,1％、Pb分0.005〜0.03％、H2O分0.01〜0.1
％含有されていたものを精製後は、Fe分0.003％以下、P
b分検出されず、H2O分0.005％以下にすることができ、
このめっき浴でアルミニウムめっきした場合、めっき層
を99.9％以上の高純度にすることができる。By refining the plating bath by these methods,
Fe content 0.01 to 0.1%, Pb content 0.005 to 0.03%, H 2 O content 0.01 to 0.1
% Of Fe content is 0.003% or less, P
b minute is not detected, H 2 O content can be 0.005% or less,
When aluminum plating is performed in this plating bath, the plating layer can have a high purity of 99.9% or higher.
以上のようにして精製すると、被めっき物へのめっき
の際の浴温を０〜150℃にしても、また、電流密度を0.1
〜30A/dm2にしても、めっき層は、緻密で、しかも粉末
状デンドライト組織にはならない。浴温を０℃より低く
すると、高電流密度でのめっきが困難になる。また、浴
温を150℃より高くし、かつ電流密度を30A/dm2より高く
すると、めっき層が灰色になって、外観が劣ってしま
い、めっき層の加工性も低下する。By refining as described above, even if the bath temperature during plating on the object to be plated is set to 0 to 150 ° C., the current density is set to 0.1
Even at ~ 30 A / dm 2 , the plating layer is dense and does not have a powdery dendrite structure. When the bath temperature is lower than 0 ° C., plating at high current density becomes difficult. Further, when the bath temperature is higher than 150 ° C. and the current density is higher than 30 A / dm 2 , the plating layer becomes gray, the appearance is deteriorated, and the workability of the plating layer is deteriorated.
めっき浴は、酸素や水分に触れても安全であるが、ア
ルミニウム錯イオンの酸化を防止するため、めっきは乾
燥無酸素雰囲気中（たとえば乾燥N2やAr中）で行なう。
また電流は、直流、パルス電流のいずれでもよいが、パ
ルス電流の方が結晶が微細になり、加工性が良好にな
る。The plating bath is safe even if it is exposed to oxygen and water, but plating is performed in a dry oxygen-free atmosphere (for example, in dry N 2 or Ar) in order to prevent oxidation of aluminum complex ions.
The current may be either direct current or pulsed current, but the pulsed current provides finer crystals and better workability.
ところで連続めっきで均一なめっきを行うためには、
めっき浴にAlイオンを補給して、浴中のAlイオンを一定
に管理する必要があるが、この場合、本発明のめっき浴
では陽極をAl製可溶性陽極にすると、通電量に応じてAl
イオンが自動的に補給されるので、好都合である。By the way, in order to perform uniform plating with continuous plating,
It is necessary to replenish the plating bath with Al ions to control the Al ions in the bath to a constant level. In this case, in the plating bath of the present invention, if the anode is an Al-made soluble anode, Al is converted according to the amount of electricity supplied.
This is convenient because the ions are automatically replenished.
陽極にTi−Pt系などの不溶性陽極を使用して連続めっ
きする場合のAlイオンの補給は、AlCl3、AlBr3、AlI3な
どのハロゲン化物を補給すればよい。この場合、補給ハ
ロゲン化物の精製を必要とするが、精製は、めっき浴外
部にハロゲン化物の補給槽を設けて、この補給槽とめっ
き浴との間に精製槽を設けて、この精製槽で先に述べた
方法により行えばよい。しかし、不溶性陽極使用による
連続めっきの場合、電解時に陽極界面でハロゲンガス発
生反応が起こる。When continuously plating using an insoluble anode such as a Ti—Pt system as the anode, the Al ions may be replenished by halides such as AlCl 3 , AlBr 3 , and AlI 3 . In this case, it is necessary to purify the replenishment halide, but for purification, a halide replenishment tank is provided outside the plating bath, and a refining tank is provided between this replenishment tank and the plating bath. The method described above may be used. However, in the case of continuous plating using an insoluble anode, a halogen gas generating reaction occurs at the anode interface during electrolysis.
以下実施例により本発明を説明する。 The present invention will be described below with reference to examples.
（実施例） 実施例１ N2雰囲気に保ったAlCl367モル％とブチルピリジニウ
ムクロリド33モル％からなる溶融塩めっき浴の両極をア
ルミニウム板（純度99.99wt％、板厚5mm）にして、浴温
60℃、0.1A/dm2で３時間予備電解し、精製した。その後
このめっき浴を用いて、常法により溶剤蒸気洗浄、アル
カリ脱脂および酸洗などのめっき前処理を施した冷延鋼
板（板厚0.5mm）を乾燥後直ちに浸漬して、アルミニウ
ムめっきを行なった。めっきは、精製の際のアルミニウ
ム板陰極を冷延鋼板に変え、浴温60℃で直流により電流
密度10A/dm2で２分間行なった。(Example) Example 1 Both electrodes of a molten salt plating bath consisting of 67 mol% AlCl 3 and 33 mol% butylpyridinium chloride kept in an N 2 atmosphere were made into aluminum plates (purity 99.99 wt%, plate thickness 5 mm), and the bath was prepared. Warm
Preliminary electrolysis was performed at 60 ° C. and 0.1 A / dm 2 for 3 hours for purification. Then, using this plating bath, cold-rolled steel sheet (plate thickness: 0.5 mm) that had been subjected to plating steam pre-treatment such as solvent vapor cleaning, alkali degreasing and pickling by a conventional method was immediately dipped after drying to perform aluminum plating. . The plating was carried out by changing the aluminum plate cathode used for refining to a cold rolled steel plate and applying a direct current at a bath temperature of 60 ° C. and a current density of 10 A / dm 2 for 2 minutes.
得られたアルミニウムめっき鋼板のめっき層純度は、
99.99％で、厚みが均一で、白色を呈し、結晶は緻密で
あった。また鋼板に繰り返し折り曲げを施してもクラッ
クや剥離は発生せず、加工、密着性とも良好であった。The plating layer purity of the obtained aluminum-plated steel sheet is
At 99.99%, the thickness was uniform and white, and the crystals were dense. Further, even if the steel sheet was repeatedly bent, cracks and peeling did not occur, and the processing and adhesion were good.
実施例２ 実施例１で精製しためっき浴を用いて、パルス電流に
より板厚0.5mmの冷延鋼板にアルミニウムめっきを施し
た。冷延鋼板としてな、実施例１と同様の前処理を施し
たものを用い、この鋼板を陰極、アルミニウム板（実施
例１と同じ）を陽極にした。パルス電流によるめっき
は、いずれのめっき浴の場合もデューティー比1/10〜1/
100、平均電流密度0.1〜30A/dm2で行なった。その結
果、めっき層の厚みは、均一で、外観、加工性、密着性
とも直流によりめっきした場合と同一であった。また、
めっき層純度は99.98％以上であった。Example 2 Using the plating bath purified in Example 1, a cold-rolled steel sheet having a plate thickness of 0.5 mm was subjected to aluminum plating by pulse current. A cold-rolled steel sheet, which had been subjected to the same pretreatment as in Example 1, was used, and this steel sheet was used as a cathode and an aluminum plate (same as in Example 1) was used as an anode. Duty ratio of 1/10 to 1/1 /
100, average current density 0.1 to 30 A / dm 2 . As a result, the thickness of the plating layer was uniform, and the appearance, workability, and adhesion were the same as those obtained by direct current plating. Also,
The plating layer purity was 99.98% or higher.
またCu合金、Ni合金へも上記同様にめっきしてみた
が、純度99.9％以上のAlめっきが可能であった。In addition, Cu alloy and Ni alloy were plated in the same manner as above, but Al plating with a purity of 99.9% or more was possible.
比較例 実施例１と同一の前処理を施した冷延鋼板をN2雰囲気
に保ったAlCl367モル％とブチルピリジニウムクロリド3
3モル％からなる未精製溶融塩めっき浴を用いて、実施
例１と同様の前処理を施した板厚0.5mmの冷延鋼板（同
板厚）を陰極、アルミニウム板（実施例１に同じ）を陽
極として、浴温80℃、直流により電流密度20a/dm21分間
でアルミニウムめっきを行った。このめっき鋼板の外観
は、灰色を呈し、結晶は粗く、めっき層純度は99.0％で
あった。Comparative Example A cold rolled steel sheet subjected to the same pretreatment as in Example 1 was kept in N 2 atmosphere with 67 mol% of AlCl 3 and butylpyridinium chloride 3.
A cold-rolled steel sheet (same thickness) with a thickness of 0.5 mm, which was pretreated in the same manner as in Example 1 using an unpurified molten salt plating bath containing 3 mol%, was used as a cathode and an aluminum plate (same as in Example 1). Was used as an anode, and aluminum was plated at a bath temperature of 80 ° C. and a direct current of 20 a / dm 2 for 1 minute. The appearance of this plated steel sheet was gray, the crystals were rough, and the plating layer purity was 99.0%.
（効果） 以上のように、本発明によれば、純度が99.9％以上
で、組織が緻密、加工性の良好なアルミニウムめっきを
行うことができる。従って、めっき製品は、アルミニウ
ム線との良好なボンディング性を必要とするICリードフ
レームなどのような電子部品、アルマイト処理によるポ
アーを利用する磁気ディスクなどのような精密製品に使
用することができる。(Effect) As described above, according to the present invention, aluminum plating having a purity of 99.9% or more, a dense structure, and good workability can be performed. Therefore, the plated product can be used for precision parts such as electronic parts such as IC lead frames that require good bonding properties with aluminum wires and magnetic disks that utilize pores formed by alumite treatment.
また、浴温、電流密度を従来より著しく高くしても、
めっき上問題が生じないので、高速めっきが可能であ
り、連続めっきの場合の生産性を高め、めっきコストを
低減させることができる。Also, even if the bath temperature and current density are significantly higher than before,
Since no problem occurs in plating, high-speed plating is possible, productivity in the case of continuous plating can be improved, and plating cost can be reduced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 赤間 良三 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社新材料研究所内 (56)参考文献 特開 昭62−70592（ＪＰ，Ａ) 特開 昭62−70593（ＪＰ，Ａ) 特開 昭61−243190（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Ryozo Akama Inventor, Ryozo Akama 1 at 7 Takaya-shinmachi, Ichikawa-shi, Chiba Nisshin Steel Co., Ltd., New Materials Research Center (56) Reference JP-A-62-70592 (JP, A) Kai 62-70593 (JP, A) JP 61-243190 (JP, A)
Claims (3)
ＸはCl、Br、Ｉ）50〜80モル％とアルキルピリジニウム
ハロゲン化物（C5H5N−RX、但し、Ｒは炭素数１〜５の
アルキル基、Ｘはハロゲン原子）20〜50モル％とからな
る溶融塩浴またはこの浴に有機溶剤を配合したものを両
極に金属アルミニウムを用いて0.5A/dm2以下の電流密度
で予備電解することにより精製し、その後被めっき物に
アルミニウムを電気めっきすることを特徴とする電気ア
ルミニウムめっき方法。1. An aluminum halide (AlX 3 , provided that
X is Cl, Br, I) 50 to 80 mol% and an alkylpyridinium halide (C 5 H 5 N-RX, where R is an alkyl group having 1 to 5 carbon atoms and X is a halogen atom) 20 to 50 mol% A molten salt bath consisting of or and a mixture of this bath and an organic solvent are purified by pre-electrolyzing at a current density of 0.5 A / dm 2 or less using metallic aluminum on both electrodes, and then aluminum is electroplated on the object to be plated. A method for electroplating aluminum, which comprises plating.
ＸはCl、Br、Ｉ）50〜80モル％とアルキルピリジウムハ
ロゲン化物（C5H5N−RX、但し、Ｒは炭素数１〜５のア
ルキル基、Ｘはハロゲン原子）20〜50モル％とからなる
溶融塩浴またはこの浴に有機溶剤を配合したものを両極
に金属アルミニウムを用いて0.5A/dm2以下の電流密度で
電解することにより精製し、その後乾燥無酸素雰囲気中
で直流電流またはパルス電流により浴温０〜150℃、電
流密度0.1〜30A/dm2の電解条件で被めっき物にアルミニ
ウムを電気めっきすることを特徴とする電気アルミニウ
ムめっき方法。2. An aluminum halide (AlX 3 , provided that
X is Cl, Br, I) 50 to 80 mol% and alkylpyridium halide (C 5 H 5 N-RX, where R is an alkyl group having 1 to 5 carbon atoms, X is a halogen atom) 20 to 50 mol % Molten salt bath or a mixture of this bath and an organic solvent is electrolyzed at a current density of 0.5 A / dm 2 or less using metallic aluminum on both electrodes and then purified by direct current in a dry oxygen-free atmosphere. An electroaluminum plating method comprising electroplating aluminum on an object to be plated under an electrolytic condition of a bath temperature of 0 to 150 ° C. and a current density of 0.1 to 30 A / dm 2 by an electric current or a pulse current.
際、陽極を金属アルミニウムにしてめっきすることを特
徴とする特許請求の範囲第２項に記載の電気アルミニウ
ムめっき方法。3. The electroaluminum plating method according to claim 2, wherein the aluminum is electroplated on the object to be plated, and the anode is made of metal aluminum.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62174522A JP2540110B2 (en) | 1987-07-13 | 1987-07-13 | Electro aluminum plating method |
| US07/269,142 US4966660A (en) | 1987-07-13 | 1988-06-30 | Process for electrodeposition of aluminum on metal sheet |
| DE8888906056T DE3875943T2 (en) | 1987-07-13 | 1988-06-30 | METHOD FOR ELECTROPLATING A METAL LAYER WITH ALUMINUM. |
| EP88906056A EP0323520B1 (en) | 1987-07-13 | 1988-06-30 | Process for electroplating metal plate with aluminum |
| PCT/JP1988/000658 WO1989000616A1 (en) | 1987-07-13 | 1988-06-30 | Process for electroplating metal plate with aluminum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62174522A JP2540110B2 (en) | 1987-07-13 | 1987-07-13 | Electro aluminum plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6417889A JPS6417889A (en) | 1989-01-20 |
| JP2540110B2 true JP2540110B2 (en) | 1996-10-02 |
Family
ID=15979995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62174522A Expired - Lifetime JP2540110B2 (en) | 1987-07-13 | 1987-07-13 | Electro aluminum plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2540110B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010036758A3 (en) * | 2008-09-29 | 2010-06-03 | Hurst William D | Alloy coating apparatus and metalliding method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1121694A (en) * | 1997-04-10 | 1999-01-26 | Heriosu:Kk | Metallic tube housed wire, metallic pipe to house wire, and manufacture and manufacturing device of metallic pipe housed wire |
| JP6795809B2 (en) * | 2016-07-14 | 2020-12-02 | 野村興産株式会社 | Sodium manufacturing method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61243190A (en) * | 1985-04-19 | 1986-10-29 | Sumitomo Metal Ind Ltd | Electroplating method with molten slat bath |
| JPS6270593A (en) * | 1985-09-20 | 1987-04-01 | Nisshin Steel Co Ltd | Aluminum electroplating bath and plating method by said plating bath |
| JPH0613758B2 (en) * | 1985-09-20 | 1994-02-23 | 日新製鋼株式会社 | Electro aluminum plating method |
-
1987
- 1987-07-13 JP JP62174522A patent/JP2540110B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010036758A3 (en) * | 2008-09-29 | 2010-06-03 | Hurst William D | Alloy coating apparatus and metalliding method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6417889A (en) | 1989-01-20 |
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