JPS6157400B2 - - Google Patents
Info
- Publication number
- JPS6157400B2 JPS6157400B2 JP14475079A JP14475079A JPS6157400B2 JP S6157400 B2 JPS6157400 B2 JP S6157400B2 JP 14475079 A JP14475079 A JP 14475079A JP 14475079 A JP14475079 A JP 14475079A JP S6157400 B2 JPS6157400 B2 JP S6157400B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- rhodium
- sulfuric acid
- plating solution
- tank
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】
本発明は硫酸ロジウムめつき液、特にロジウム
を析出して増量した遊離硫酸を透析除去して再生
し、めつき液としての安定化を計る方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rhodium sulfate plating solution, and particularly to a method for stabilizing the solution as a plating solution by removing free sulfuric acid, which has increased in volume through dialysis, by dialysis.
電気接点をはじめ電子・電気機器や光学機械な
どの工業的用途や、装飾用としてのロジウムめつ
きは、一般に、硫酸ロジウムめつき液が広く使用
されている。第１図は一般的なロジウムめつき装
置の概要であり、図中１はめつき槽、２はめつき
液貯留槽、３は被めつき物、４は陽極板、５はめ
つき電源、６は硫酸ロジウムめつき液である。 Generally, rhodium sulfate plating liquid is widely used for rhodium plating for industrial applications such as electrical contacts, electronic/electrical equipment, and optical machines, and for decorative purposes. Figure 1 shows an outline of a general rhodium plating device.In the figure, 1 is a plating tank, 2 is a plating liquid storage tank, 3 is a plating object, 4 is an anode plate, 5 is a plating power supply, and 6 is sulfuric acid. Rhodium plating liquid.
めつき槽１内のめつき液６に所定に垂下する被
めつき物３は、めつき電源５の陰極に接続され、
めつき電源５の陽極には、めつき槽１内のめつき
液６に浸漬されたところの少なくとも表面に白金
層を形成した陽極板４が接続される。 The object to be plated 3 hanging down in a predetermined manner into the plating liquid 6 in the plating tank 1 is connected to the cathode of the plating power source 5,
Connected to the anode of the plating power source 5 is an anode plate 4 immersed in the plating solution 6 in the plating tank 1 and having a platinum layer formed on at least its surface.
一方、ポンプ７によつて貯留槽２からめつき槽
１の下部に流入しためつき液６は、一定液面レベ
ルと所要の流を作つてめつき槽１の上部からオー
バー・フローし、貯留槽２に還流するようにな
る。 On the other hand, the plating liquid 6 flowing into the lower part of the plating tank 1 from the storage tank 2 by the pump 7 overflows from the upper part of the plating tank 1 by creating a constant liquid level and a required flow, and then flows into the storage tank. It becomes reflux to 2.
かかる構成のめつき装置において、めつき液６
を所定に循環し、めつき電源５の回路を閉じる
と、めつき電流が被めつき物３と陽極板４の間に
流れる。その結果、硫酸ロジウム例えばRh2
（SO4）3は電気分解して、Rhが被めつき物３の表
面に析出してロジウムめつき層を形成し、SO4は
遊離硫酸を作つてめつき液６中に残る。 In the plating apparatus having such a configuration, the plating liquid 6
When the plating current is circulated in a predetermined manner and the circuit of the plating power source 5 is closed, a plating current flows between the plated object 3 and the anode plate 4. As a result, rhodium sulfate e.g. Rh 2
(SO 4 ) 3 is electrolyzed, Rh is deposited on the surface of the plated object 3 to form a rhodium plating layer, and SO 4 produces free sulfuric acid and remains in the plating solution 6.
即ち、めつき液中の遊離硫酸が次第に増量され
て、めつき効率は低下するのみならず、前記遊離
硫酸が不純物を溶解してめつき液６の純度を悪化
させ、ロジウムめつき品位が低められる欠点があ
つた。そのため、従来はめつき液中の遊離硫酸濃
度が３倍程度になると、めつき液を廃液処分にし
ていた。しかし、前記廃液中には、まだ相当量の
硫酸ロジウムが残存しており、極めて不経済的で
あつた。その対策として前記廃液中にバリウムを
投入し、バリウムと遊離硫酸を結合させて硫酸バ
リウムを作り沈降させて、硫酸を除去する方法も
あるが、H2SO4＋Ba（OH）2・8H2O→BaSO4＋
10H2O硫酸除去効率が悪く、かつ、硫酸バリウム
除去処理が複雑であるため実用的でなかつた。 That is, the amount of free sulfuric acid in the plating solution is gradually increased, and not only does the plating efficiency decrease, but also the free sulfuric acid dissolves impurities and deteriorates the purity of the plating solution 6, resulting in a lower rhodium plating quality. It had some drawbacks. Therefore, conventionally, when the concentration of free sulfuric acid in the plating solution tripled, the plating solution was disposed of as waste. However, a considerable amount of rhodium sulfate still remained in the waste liquid, making it extremely uneconomical. As a countermeasure, there is a method to remove sulfuric acid by adding barium to the waste liquid and combining barium and free sulfuric acid to form barium sulfate and sedimentation . →BaSO 4+
The removal efficiency of 10H 2 O sulfuric acid was poor, and the process for removing barium sulfate was complicated, making it impractical.
本発明の目的は上記硫酸ロジウムめつき液中に
増量した遊離硫酸を経済的に除去し、めつき液の
再生を計ることであり、この目的は硫酸ロジウム
めつき液中の前記遊離硫酸は、陰イオン交換膜を
介して水に透析除去させることを特徴とする硫酸
ロジウムめつき液の再生方法を提供して達成され
る。以下、本発明に係わる一実施例のロジウムめ
つき装置を示す第２図を用いて、本発明を説明す
る。第１図と同等部分には同一符号を用いた第２
図において、耐めつき液性材料よりなる角形の透
析槽８には、横中央を垂直に仕切るようにして、
陰イオン交換膜よりなる隔壁９が設けてある。隔
壁９により仕切られた手前には、めつき槽１から
オーバー・フローしためつき液６′が流入して貯
留槽２へ流出し、隔壁９により仕切られた後方に
は、純水１０が流入して流出するようになつてい
る。 The purpose of the present invention is to economically remove the increased amount of free sulfuric acid in the rhodium sulfate plating solution and regenerate the plating solution. This is accomplished by providing a method for regenerating rhodium sulfate plating solution, which is characterized by dialysis removal of rhodium sulfate plating solution with water through an anion exchange membrane. The present invention will be described below with reference to FIG. 2, which shows a rhodium plating apparatus according to an embodiment of the present invention. Parts equivalent to those in Figure 1 are designated by the same symbols in Figure 2.
In the figure, a rectangular dialysis tank 8 made of a liquid-based material that is resistant to corrosion is partitioned vertically in the horizontal center.
A partition wall 9 made of an anion exchange membrane is provided. The overflowing plating liquid 6' from the plating tank 1 flows into the front side partitioned by the partition wall 9 and flows out to the storage tank 2, and the pure water 10 flows into the rear side partitioned by the partition wall 9. It is starting to leak out.
即ち、めつき槽１において、ロジウム（Rh）
が析出され、遊離硫酸濃度が高められためつき液
６′は、透析槽８に流入して透析槽８から流出す
る間に、隔壁９を介して接する純水１０に遊離硫
酸が透析吸収される。従つて透析槽８から流出さ
れ、貯留槽２に貯留されためつき液６″は、再生
されて遊離硫酸濃度の低められたものになつてお
り、再度ポンプ７にてめつき槽１に送られて、被
めつき物３のロジウムめつきに寄与する。 That is, in plating tank 1, rhodium (Rh)
is precipitated and the concentration of free sulfuric acid is increased. While the solution 6' flows into the dialysis tank 8 and flows out from the dialysis tank 8, the free sulfuric acid is dialyzed and absorbed by the pure water 10 that is in contact with it through the partition wall 9. . Therefore, the plating solution 6'' discharged from the dialysis tank 8 and stored in the storage tank 2 is regenerated and has a reduced concentration of free sulfuric acid, and is sent to the plating tank 1 again by the pump 7. This contributes to the rhodium plating of the plated object 3.
なお、上記実施例において、貯留槽と透析槽と
はそれぞれ独立させてあるが、両者を一体化構
造、即ち貯留槽の中を陰イオン交換膜よりなる隔
壁にて仕切り、一方は純水を流し、他方にはめつ
き液を貯留し、そのめつき液をポンプにてめつき
槽へ送るようにしてもよい。また、透析槽内のめ
つき液及び純水をそれぞれ撹拌器にて常時撹拌
し、前記隔壁に接する流れを強めれば、遊離硫酸
の透析効率を高めることができる。さらに、前記
透析処理はめつき中又はめつき休止中の何れかの
時間に行なつてもよいし、遊離硫酸量の増加があ
まり多くない場合には、適宜増量されるのを待つ
て実施することができる。 In the above example, the storage tank and the dialysis tank are each independent, but they are integrated into one structure, that is, the storage tank is partitioned by a partition wall made of an anion exchange membrane, and one has pure water flowing through it. , the plating liquid may be stored in the other, and the plating liquid may be sent to the plating tank by a pump. Furthermore, the efficiency of dialysis of free sulfuric acid can be increased by constantly stirring the plating solution and pure water in the dialysis tank using a stirrer to strengthen the flow in contact with the partition wall. Further, the dialysis treatment may be carried out either during plating or during a plating pause, or if the amount of free sulfuric acid does not increase significantly, it may be carried out after waiting for the amount to be increased appropriately. I can do it.
以上説明したように、本発明による硫酸ロジウ
ムめつき液の再生方法は、従来構造のめつき装置
に簡単な装置を付加して容易に実施可能であり、
かつ、効率よく増量硫酸が除去できるため、めつ
き液中の成分比が狭い範囲で制御可能となり、安
定しためつき膜が得られる。更に従来よりもめつ
き液中に不純物が溶解され難くなつたことにより
めつき液寿命が高められた経済的効果は極めて大
きい。 As explained above, the method for regenerating rhodium sulfate plating solution according to the present invention can be easily carried out by adding a simple device to a plating device of conventional structure.
In addition, since the bulk sulfuric acid can be removed efficiently, the component ratio in the plating solution can be controlled within a narrow range, and a stable plating film can be obtained. Furthermore, since impurities are less likely to be dissolved in the plating solution than in the past, the life of the plating solution is extended, which has an extremely large economical effect.
第１図は、従来の一般的なロジウムめつき装
置、第２図は本発明に係わる一実施例のロジウム
めつき装置概要図。
６，６′，６″……めつき液、９……隔壁（陰イ
オン交換膜）、１０……純水。
FIG. 1 is a general diagram of a conventional rhodium plating apparatus, and FIG. 2 is a schematic diagram of an embodiment of a rhodium plating apparatus according to the present invention. 6, 6', 6''...Plating liquid, 9...Partition wall (anion exchange membrane), 10...Pure water.
Claims (1)
ロジウムめつき液の再生方法において、前記めつ
き液中の前記遊離硫酸を、陰イオン交換膜を介し
て水に透析除去させることを特徴とする硫酸ロジ
ウムめつき液の再生方法。1. A method for regenerating a rhodium sulfate plating solution in which rhodium is precipitated to increase the amount of free sulfuric acid, characterized in that the free sulfuric acid in the plating solution is removed by dialysis against water through an anion exchange membrane. How to regenerate rhodium plating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14475079A JPS5669400A (en) | 1979-11-08 | 1979-11-08 | Regenerating method for rhodium sulfate plating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14475079A JPS5669400A (en) | 1979-11-08 | 1979-11-08 | Regenerating method for rhodium sulfate plating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5669400A JPS5669400A (en) | 1981-06-10 |
| JPS6157400B2 true JPS6157400B2 (en) | 1986-12-06 |
Family
ID=15369495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14475079A Granted JPS5669400A (en) | 1979-11-08 | 1979-11-08 | Regenerating method for rhodium sulfate plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5669400A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014034691A (en) * | 2012-08-07 | 2014-02-24 | Mitsubishi Materials Corp | Recycling method and apparatus of plating solution |
-
1979
- 1979-11-08 JP JP14475079A patent/JPS5669400A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5669400A (en) | 1981-06-10 |
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