JPH01104795A - Method for controlling atmosphere in electrolytic aluminizing tank - Google Patents
Method for controlling atmosphere in electrolytic aluminizing tankInfo
- Publication number
- JPH01104795A JPH01104795A JP26049587A JP26049587A JPH01104795A JP H01104795 A JPH01104795 A JP H01104795A JP 26049587 A JP26049587 A JP 26049587A JP 26049587 A JP26049587 A JP 26049587A JP H01104795 A JPH01104795 A JP H01104795A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- tank
- plating tank
- oxygen concentration
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、塩化アルミニウムとブチルピリジニウムクロ
リドとの溶融塩浴の雰囲気を管理して、めっ！浴の劣化
を防止する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention provides a method for controlling the atmosphere of a molten salt bath of aluminum chloride and butylpyridinium chloride, and for producing metal chloride. This invention relates to a method for preventing bath deterioration.
（従来技術）
塩化アルミニウムとブチルピリゾニウムクロリドとは、
それぞれ５０〜７５モル％と２５〜５０モル％の割合で
混合すると、溶融し、常温でも液体となり、アルミニウ
ムがＡｌＣ１，−や＾１．ＣＬ−イオンに解離するので
、アルミニウムの電気めっきを行うことができる。この
めっき浴は、発火、爆発等の危険がなく、めっき光沢を
高くしたい場合にベンゼン、トルエン、キシシンなどの
有機ｍｔｍ ｔｔ添加する場合もあるが、それでも他の
非水溶を系めっき液に比べ安全である。(Prior art) What is aluminum chloride and butylpyrizonium chloride?
When mixed at a ratio of 50 to 75 mol% and 25 to 50 mol%, respectively, they melt and become liquid even at room temperature, and aluminum becomes AlC1,- or ^1. Since it dissociates into CL- ions, electroplating of aluminum can be performed. This plating bath has no danger of ignition or explosion, and organic mtm tt such as benzene, toluene, or xycin may be added to it to increase the gloss of the plating, but it is still safer than other non-aqueous plating solutions. It is.
−Ｌかし、このめり％ｉｌｌは、空気に触れると、上記
イーオンが酸化されるため、めっき時やめっ！＆液の保
管の際、゛窒素やアルゴンなどの不活性がスを常時めっ
き槽内に流し、めっｔｋＷ３内が外気に対してプラス圧
になるようにしていた。-L, do not use this method when plating, as the above ions will be oxidized when exposed to air! & When storing the solution, an inert gas such as nitrogen or argon was constantly flowed into the plating tank to maintain a positive pressure inside the plating tank tkW3 relative to the outside air.
（発明が解決しようとする問題点）
しかしながら、このように不活性ガスを常時流し続ける
と、不活性ガス費用が多頷になり、めっき費が高くなる
ものであった。このため、工業的に実施するにあ７たっ
ては、不活性ガスの使用１を少なくする必要があった。(Problems to be Solved by the Invention) However, if the inert gas is kept flowing in this way, the cost of the inert gas increases and the plating cost increases. Therefore, for industrial implementation, it was necessary to reduce the amount of inert gas used.
（問題点を解決するための手段）
そこで、本発明は、不活性ガスを循環使用するよう、に
した。すなわち、本発明は、塩化アルミニウムとプチル
ビリジニウムクロリ゛ドとの溶ｉ塩浴またはこの浴に有
機溶媒を添加した浴を収容し、雰囲気として不活性ガス
が充たされた密閉型めっき槽の雰囲気中酸素濃度を管理
する際、雰囲□気ガスを槽外に取り出して、塩素もしく
は塩化物のがスを除去した後、酸素濃度計により酸素濃
度を測定し、その後ガスをめっき槽に返す循環回路をめ
っき槽外部に設けで、雰囲気ガス中の酸素濃度を管理す
るようにした。(Means for Solving the Problems) Therefore, the present invention uses an inert gas in a circular manner. That is, the present invention provides a closed plating tank containing a molten salt bath of aluminum chloride and butylpyridinium chloride or a bath prepared by adding an organic solvent to this bath, and filled with an inert gas as an atmosphere. When controlling the oxygen concentration in the atmosphere, the atmosphere gas is taken out of the plating tank, chlorine or chloride gas is removed, the oxygen concentration is measured using an oxygen concentration meter, and then the gas is introduced into the plating tank. A return circulation circuit was installed outside the plating tank to control the oxygen concentration in the atmospheric gas.
一般に、めっさ槽内雰囲気の酸素濃度測定は、不活性ガ
ス放出管から放出される雰囲気ガスを酸素濃度計で測定
すればできる。しかし、この方法では酸素濃度計取り付
けの際、放出管から空気が混入する恐れがある。Generally, the oxygen concentration in the atmosphere inside the plating tank can be measured by measuring the atmospheric gas released from the inert gas discharge pipe with an oxygen concentration meter. However, with this method, there is a risk that air may get mixed in from the discharge pipe when installing the oxygen concentration meter.
また、塩化アルミニウムとブチルピリジニウムクロリド
との溶融塩浴は、塩素や塩化物のガスを発生し、塩化物
の一部゛は不活性〃二中に含まれる水分と反応して塩化
水素ガスになる。さらに、可溶性陽極（金属Δ１）を用
いてめっきする場合、電流密度を極端に高くしなければ
、陽極より塩素ガスが発生することがないが、電流密度
を極端に高くしたり、陽極を不陽性陽極伸したりすると
、塩素ガスが発生する。従って、雰囲気がスを直接酸素
濃度計で測定すると、濃度計のセルが塩素や塩化物のが
スで汚染されたり、腐食されたりして、測定値が不正確
になる。In addition, a molten salt bath of aluminum chloride and butylpyridinium chloride generates chlorine and chloride gas, and some of the chloride reacts with the moisture contained in the inert mixture to become hydrogen chloride gas. . Furthermore, when plating with a soluble anode (metal Δ1), chlorine gas will not be generated from the anode unless the current density is extremely high. When the anode is stretched, chlorine gas is generated. Therefore, if atmospheric gas is directly measured with an oxygen concentration meter, the cell of the concentration meter may be contaminated or corroded by chlorine or chloride gas, making the measured value inaccurate.
そこで、本発明で−は、雰ＦＭ気ガスをめっき槽外に取
り出して循環させるとともに、その循環の際、まず塩素
や塩化物のガスを除去し、次に酸素濃度計で酸素を測定
するようにした。Therefore, in the present invention, the atmospheric FM gas is taken out of the plating tank and circulated, and during the circulation, chlorine and chloride gases are first removed, and then oxygen is measured using an oxygen concentration meter. I made it.
ユニで、塩素や塩化物のガスを除去するには、吸着剤、
例えば、活性炭、活性アルミナ、活性白土、ケイ藻土、
カオリン、合成ゼオライトなどをを使用すればよい。ま
た、酸素濃度計としては、ＩＩ Ｅ ＲＲＭ＾ｌｊ Ｍ
Ｏ１１１ＴＺ製０＾１５００型などを使用すればよい。To remove chlorine and chloride gases, use an adsorbent,
For example, activated carbon, activated alumina, activated clay, diatomaceous earth,
Kaolin, synthetic zeolite, etc. may be used. In addition, as an oxygen concentration meter, II E RRM^lj M
The 0^1500 type manufactured by O111TZ may be used.
塩化アルミニウムとブチルピリジニウムクロリドとのめ
っき浴は、雰囲気中に酸素が全く含まれないようにする
必要はなく、１０００ ｐ’ｐｍ程度含 １まれてい
てもイオンが酸化されることがない。The plating bath of aluminum chloride and butylpyridinium chloride does not need to be completely free of oxygen in the atmosphere, and even if about 1000 p'pm of oxygen is present, the ions will not be oxidized.
（実施例）
第１図は、本発明による塩化アルミニウムとブチルピリ
ジニウムクロリドとのめっき浴の＄囲気ｆ理方法を示す
図で、１は密閉型のめっき槽である。このめっき槽１の
中には、通常、塩化アルミニウム５０〜７５モル％とプ
チルビリクニウムクロリド２５〜５０モル％のめっき液
２またはこれに有機溶媒を添加しためっき液２が収容さ
れ、上部空間には不活性ガスが充たされている。そして
、 。(Example) FIG. 1 is a diagram illustrating a method for plating a plating bath of aluminum chloride and butylpyridinium chloride according to the present invention, and 1 is a closed type plating tank. This plating tank 1 normally contains a plating solution 2 containing 50 to 75 mol% of aluminum chloride and 25 to 50 mol% of butylbilicnium chloride, or a plating solution 2 to which an organic solvent is added, and the upper space is is filled with inert gas. and, .
上部空間には、従来のように、不活性がスボンベ３と放
出？Ｆ４とが接続されている。In the upper space, as in the past, inert gas is released from the cylinder 3? F4 is connected.
このめっき槽１の雰囲気を管理するには、上部に循環′
ｒＩ５を接続して、この循環管５に雰囲気の出側よりバ
ルブ６、゛ポンプ７、バルブ８．８ａ。In order to control the atmosphere of this plating tank 1, there is a circulation system at the top.
rI5 is connected, and the valve 6, pump 7, and valve 8.8a are connected to the circulation pipe 5 from the atmosphere outlet side.
吸着剤を充填した吸着＃Ｊ９．９ａ、自動酸′Ｘ濃度計
１０およびバルブ１１を取り付ける。なお、バルブ８．
８ａと吸着筒９．９ａとは、循環？ｉ’ ５の一部を分
岐させて、並列に取り付ける。また、自動酸素濃度計１
０には、レコーダー１２を接続し、常に酸素濃度を記録
できるようにする。Attach adsorption #J9.9a filled with adsorbent, automatic acid 'X concentration meter 10 and valve 11. In addition, valve 8.
8a and adsorption cylinder 9.9a are circulation? Part of i' 5 is branched and installed in parallel. In addition, automatic oxygen concentration meter 1
0 is connected to a recorder 12 so that the oxygen concentration can be recorded at all times.
この方法で雰囲気中の酸素濃度を測定するには、バルブ
８．８１１のいずれか一方を除いて、すべてのバルブを
開き、ポンプ７で雰囲気を吸引して循環させる。バルブ
８．８ａのいずれか一方を閉じておくのは、吸着筒９．
９ａを交互に使用し、−方の能力が低下した場合、・他
方に切り替えるためである。 、： ・ −
−、・ ゛酸素濃度に異常があった場合には、不活性ガ
スボンベ３より不活性ガスを供給して、゛雰囲気ガスを
放出管４より放出させる。・ゝ”
この方法により吸着筒９ζ９ａに活性炭を２０９充填し
、金属ＡＩを陽極にして電流密度１八／ｄ＋ａ”で電気
めっきしながら、めっき槽１の窒素雰囲気ガスを５０
＋ｎｌ／＋＋＋ｉｎの割合で循環管５内を循環させ、吸
着筒９通過後のガスを硝酸銀溶液に放出したが、白濁し
なかった。また、自動酸素濃度計１０による酸素濃度は
１００ｐｐ＋ａであった。To measure the oxygen concentration in the atmosphere using this method, all valves except one of the valves 8 and 811 are opened, and the atmosphere is sucked and circulated by the pump 7. One of the valves 8.8a is kept closed by the adsorption tube 9.
This is because 9a are used alternately, and when the - one's ability decreases, it is possible to switch to the other one. , : ・ −
-, If there is an abnormality in the oxygen concentration, inert gas is supplied from the inert gas cylinder 3, and atmospheric gas is released from the discharge pipe 4.・ゝ'' By this method, the adsorption column 9ζ9a is filled with 209% activated carbon, and while electroplating is carried out at a current density of 18/d+a'' using the metal AI as an anode, the nitrogen atmosphere gas in the plating tank 1 is filled with 50% activated carbon.
The silver nitrate solution was circulated through the circulation tube 5 at a rate of +nl/+++in, and the gas after passing through the adsorption cylinder 9 was released into the silver nitrate solution, but it did not become cloudy. Further, the oxygen concentration measured by the automatic oxygen concentration meter 10 was 100 pp+a.
また、めっき液保管中に窒素雰囲気がスを上記循環条件
で１００時間循環させ、硝酸銀：８液により吸着通過９
ａ通過後のガス中の塩素、塩化物を確認したが、認めら
れず、自動酸素濃度計１０による酸素濃度は１００ ｐ
ｐｍと一定であった。In addition, during storage of the plating solution, a nitrogen atmosphere was circulated for 100 hours under the above circulation conditions, and silver nitrate: 8 liquid adsorbed and passed 9
I checked for chlorine and chloride in the gas after passing through a, but none were found, and the oxygen concentration measured by the automatic oxygen concentration meter 10 was 100p.
It was constant at pm.
（発明の効果）
以上のように、本発明によれば、塩化アルミニウムとブ
チルピリジニウムクロリドとの溶融塩を用いる電気アル
ミニウムめっき浴の雰囲気を管理することができ、しか
も、不活性ガスは、循環させる方法であるため、浪費せ
ず、めっき費用が安価になる(Effects of the Invention) As described above, according to the present invention, the atmosphere of an electrolytic aluminum plating bath using a molten salt of aluminum chloride and butylpyridinium chloride can be controlled, and in addition, an inert gas can be circulated. Because it is a method, there is no waste and the plating cost is low.
第１図は、本発明による電気めっき方法を示すブロック
図である。
１・・・めっき槽、２・・・めっき液、３・・・不活性
がスポンベ、４・・・放出管、５・・・循環管、６・・
・パルプ、７、・・・ポンプ、８．８ａ・・・パルプ、
９．９ａ・・・吸着筒、１０・・・自動酸素濃度計、１
１・・・パルプ、１２・・・レコーダーFIG. 1 is a block diagram showing an electroplating method according to the present invention. 1... Plating tank, 2... Plating solution, 3... Inert sponge, 4... Discharge pipe, 5... Circulation pipe, 6...
・Pulp, 7,...Pump, 8.8a...Pulp,
9.9a...Adsorption cylinder, 10...Automatic oxygen concentration meter, 1
1...Pulp, 12...Recorder
Claims (3)
との溶融塩浴またはこの浴に有機溶媒を添加した浴を収
容し、雰囲気として不活性ガスが充たされた密閉型めっ
き槽の雰囲気中酸素濃度を管理する際、雰囲気ガスを槽
外に取り出して、塩素もしくは塩化物のガスを除去した
後、酸素濃度計により酸素濃度を測定し、その後ガスを
めっき槽に返す循環回路をめっき槽外部に設けて、雰囲
気ガス中の酸素濃度を管理することを特徴とする電気ア
ルミニウムめっき槽の雰囲気管理方法。(1) A closed plating tank containing a molten salt bath of aluminum chloride and butylpyridinium chloride or a bath with an organic solvent added thereto, and controlling the oxygen concentration in the atmosphere of a closed plating tank filled with an inert gas. During the process, atmospheric gas is taken out of the plating tank, chlorine or chloride gas is removed, the oxygen concentration is measured using an oxygen concentration meter, and a circulation circuit is installed outside the plating tank to return the gas to the plating tank. An atmosphere control method for an electrolytic aluminum plating tank characterized by controlling the oxygen concentration in the gas.
を特徴とする特許請求の範囲第１項に記載の電気アルミ
ニウムめっき槽の雰囲気管理方法。(2) The method for controlling the atmosphere of an electrolytic aluminum plating tank according to claim 1, characterized in that chlorine or hydrogen chloride gas is removed using an adsorbent.
特徴とする特許請求の範囲第１項に記載の電気アルミニ
ウムめっき槽の雰囲気管理方法。(3) The method for controlling the atmosphere of an electrolytic aluminum plating tank according to claim 1, which comprises controlling the oxygen concentration to 1000 ppm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26049587A JPH01104795A (en) | 1987-10-15 | 1987-10-15 | Method for controlling atmosphere in electrolytic aluminizing tank |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26049587A JPH01104795A (en) | 1987-10-15 | 1987-10-15 | Method for controlling atmosphere in electrolytic aluminizing tank |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01104795A true JPH01104795A (en) | 1989-04-21 |
Family
ID=17348760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26049587A Pending JPH01104795A (en) | 1987-10-15 | 1987-10-15 | Method for controlling atmosphere in electrolytic aluminizing tank |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01104795A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006507405A (en) * | 2002-06-28 | 2006-03-02 | アドバンスト・マイクロ・ディバイシズ・インコーポレイテッド | Apparatus and method for electrochemically treating a substrate while reducing metal corrosion |
| CN103261487A (en) * | 2010-09-17 | 2013-08-21 | 阿尔斯通技术有限公司 | Raw gas collection system |
| EP2891730A4 (en) * | 2012-08-31 | 2016-05-18 | Hitachi Ltd | NONAQUEOUS ELECTROLYTIC DEPOSITION METHOD AND NONAQUEOUS ELECTROLYTIC DEPOSITION APPARATUS |
-
1987
- 1987-10-15 JP JP26049587A patent/JPH01104795A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006507405A (en) * | 2002-06-28 | 2006-03-02 | アドバンスト・マイクロ・ディバイシズ・インコーポレイテッド | Apparatus and method for electrochemically treating a substrate while reducing metal corrosion |
| CN103261487A (en) * | 2010-09-17 | 2013-08-21 | 阿尔斯通技术有限公司 | Raw gas collection system |
| US9115437B2 (en) | 2010-09-17 | 2015-08-25 | Alstom Technology Ltd | Raw gas collection system |
| CN103261487B (en) * | 2010-09-17 | 2016-07-27 | 阿尔斯通技术有限公司 | Raw Gas Collection System |
| EP2891730A4 (en) * | 2012-08-31 | 2016-05-18 | Hitachi Ltd | NONAQUEOUS ELECTROLYTIC DEPOSITION METHOD AND NONAQUEOUS ELECTROLYTIC DEPOSITION APPARATUS |
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