JPS5824519B2 - How to adjust the pH of electrolytic nickel plating solution - Google Patents
How to adjust the pH of electrolytic nickel plating solutionInfo
- Publication number
- JPS5824519B2 JPS5824519B2 JP9436876A JP9436876A JPS5824519B2 JP S5824519 B2 JPS5824519 B2 JP S5824519B2 JP 9436876 A JP9436876 A JP 9436876A JP 9436876 A JP9436876 A JP 9436876A JP S5824519 B2 JPS5824519 B2 JP S5824519B2
- Authority
- JP
- Japan
- Prior art keywords
- plating solution
- value
- ion exchange
- nickel
- plating
- 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
- Treatment Of Water By Ion Exchange (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】
本発明は電解ニッケルめっきにおいて、めっき液のｐＨ
値を自動的にコントロールし、よつ漸増するニッケルイ
オンを回収し、めっき液濃度の上昇を防止する方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION In electrolytic nickel plating, the present invention provides
This invention relates to a method for automatically controlling the value of nickel ions, recovering gradually increasing nickel ions, and preventing an increase in the plating solution concentration.
電気ニッケルめっきに用いられるめっき液組成は一般的
には次のものが使用されることが多い０硫酸ニツケル（
Ｎ ｔ Ｓ ０４・６Ｈ２０） ２８０±２０９７７
！塩化ニツケル（Ｎ ｓ Ｃ４・６Ｈ２０） ４５±
５ ｇ／ｌ硼酸（Ｈ３ＢＯ３） ４０±
５ ｇ／１３その他にめっき液のｐＨ値を３．８〜４．
２の範囲に調整するための適当量の硫酸又は塩酸及びそ
の他の目的の添加物
ここでめっき条件としてＩ）Ｈ値は非常に重要であり、
ｐＨ値が高ければニッケルの水酸化物がめつき膜に含ま
れて密着性が悪くなり、逆にｐＨ値が低ければ水素発生
のためにピット（凹み）が生じ、電流効率の低下などの
不具合が生じるものである。The composition of the plating solution used in electrolytic nickel plating is generally the following: 0 nickel sulfate (
NtS 04・6H20) 280±20977
! Nickel chloride (N s C4・6H20) 45±
5 g/l boric acid (H3BO3) 40±
5 g/13 In addition, the pH value of the plating solution is 3.8 to 4.
Appropriate amount of sulfuric acid or hydrochloric acid and other additives to adjust to the range of 2. As plating conditions here, I) H value is very important,
If the pH value is high, nickel hydroxide will be included in the plating film, resulting in poor adhesion, while if the pH value is low, pits will occur due to hydrogen generation, resulting in problems such as reduced current efficiency. It is something that occurs.
ところでめっき槽の電極に通電を行えば陽極と陰極では
次の反応が起る。By the way, when electricity is applied to the electrodes of the plating bath, the following reaction occurs at the anode and cathode.
陽極 Ｎｉ＋５Ｏ４−″−−２ｅ−）ＮｉＳＯ４（イ）
Ｎｉ＋２Ｃ１−−２ｅ−）Ｎ１ＣＡ！２ （ロ）
陰極 Ｎ ｉ十＋＋２ ｅ −＋Ｎ ｉ
（ハ）２ Ｈ＋＋２ ｅ→Ｈ２↑ に）上
記の式において、陽極におけるＫＸ口）式の溶解効率は
通常は１００％近い値が得られるが、陰極においては（
ハ）式の析出効率は９７％程度であり、残りの３％はに
）式に費やされ水素ガスが発生する。Anode Ni+5O4-''--2e-) NiSO4 (a)
Ni+2C1--2e-)N1CA! 2 (b)
Cathode N i + +2 e - + N i
(c) 2 H++2 e→H2↑) In the above equation, the dissolution efficiency of the KX port) equation at the anode is usually close to 100%, but at the cathode (
The precipitation efficiency of formula (c) is about 97%, and the remaining 3% is spent in formula (c) to generate hydrogen gas.
従ってめっき液中にはニッケルイオン（Ｎｉ ” ）が
漸増し、このイオンが酸と結合して硫酸ニッケルや塩化
ニッケルとなり酸が減少するためにめっき液のｐＨ値が
上昇することになる。Therefore, nickel ions (Ni'') gradually increase in the plating solution, and these ions combine with the acid to form nickel sulfate or nickel chloride, which causes the acid to decrease and the pH value of the plating solution to rise.
したがって実際の操業においては絶えずｐＨ値を測定し
、その結果によって硫酸等を加えてｐＨ値をコントロー
ルする必要がある。Therefore, in actual operation, it is necessary to constantly measure the pH value and control the pH value by adding sulfuric acid or the like based on the results.
また一方では漸増するニッケルイオンのためにめっき液
の濃度が増加し、再結晶化の問題も生じる。On the other hand, the concentration of the plating solution increases due to the gradual increase in nickel ions, which also causes the problem of recrystallization.
従来はめつきされる品物にめっき液が付着して外部に持
出される量があるためにめっき液中のニッケルイオンの
漸増はあまり問題にならなかったが、最近においては公
害省資源対策として品物に付着するめつき液をほぼ完全
に回収するようになったために濃度増加が問題化するよ
うになり、別途に無公害化処理をしてから廃棄する必要
が生じている。In the past, the gradual increase in nickel ions in the plating solution did not pose much of a problem because some of the plating solution adhered to the items being plated and was carried out to the outside. Since the adhering plating solution has become almost completely recovered, an increase in concentration has become a problem, and it has become necessary to separately treat it to make it non-polluting before disposing of it.
本発明は以上の事情にかんがみて、めっき槽の他にｐＨ
測定槽とイオン交換樹脂塔を設置し、まずめっき液をポ
ンプによりｐＨ測定槽に送り込み、あらかじめ設定した
ｐＨ値以上ならば更にめっき液をポンプによりイオン交
換樹脂塔に送り込み、漸増した硫酸ニッケルや塩化ニッ
ケルを吸着してｐＨ値を下げ、更にこれらで飽和した樹
脂は別途に硫酸や塩酸と反応させてニッケルイオンを回
収する。In view of the above circumstances, the present invention has been developed in addition to a plating bath.
A measuring tank and an ion exchange resin tower are installed, and the plating solution is first pumped into the pH measuring tank, and if the pH value is higher than the preset value, the plating solution is further pumped into the ion exchange resin tower, and the nickel sulfate and chloride that are gradually increased are pumped into the ion exchange resin tower. The pH value is lowered by adsorbing nickel, and the resin saturated with these is separately reacted with sulfuric acid or hydrochloric acid to recover nickel ions.
一方ｐＨ値があらかじめ設定した値以下の場合はめつき
液をイオン交換樹脂塔に送ることなくめつき槽とｐＨ測
定槽の間を循環させる。On the other hand, if the pH value is below a preset value, the plating solution is circulated between the plating tank and the pH measuring tank without being sent to the ion exchange resin tower.
以上の方法によりめっき液のＩ）Ｈ値を所定の範囲内に
コントロールしかつ漸増するニッケルイオンを回収する
ものである。By the above method, the I)H value of the plating solution is controlled within a predetermined range, and nickel ions which gradually increase are recovered.
以下に本発明を実施例にもとづいて説明する。The present invention will be explained below based on examples.
第１図は本発明の実施例を模式的に図示したものである
が、めつき槽１からポンプ２によりめっき液をｐＨ測定
槽３に送り込むがｐＨ測定槽３の液面制御はフロートな
しスイッチ４によって行う。FIG. 1 schematically shows an embodiment of the present invention, in which a plating solution is sent from a plating tank 1 to a pH measuring tank 3 by a pump 2, but the liquid level in the pH measuring tank 3 is controlled by a switch without a float. 4.
ｐＨ測定槽３には通常のＩ）Ｈ測定機５が設置されてお
り、この測定結果を制御機６にインプットし、この制御
機６によりポンプ１の駆動を制御する。A normal I)H measuring device 5 is installed in the pH measuring tank 3, and the measurement results are input to a controller 6, which controls the drive of the pump 1.
即ち測定されたｐＨ値があらかじめ設定された値以上の
ときはポンプ１を駆動してめっき液を更にイオン交換塔
８に送り込む。That is, when the measured pH value is higher than a preset value, the pump 1 is driven to further send the plating solution to the ion exchange tower 8.
逆に測定されたｐＨ値が所定の範囲内に入っておれば、
めっき液をイオン交換塔に送ることなくポンプのみを駆
動させて、めっき液はめつき槽とｌ）Ｈ測定槽の間のみ
を循環する。Conversely, if the measured pH value is within the specified range,
By driving only the pump without sending the plating solution to the ion exchange tower, the plating solution is circulated only between the plating tank and the H measurement tank.
そしてこの状態で操業を続けた結果、ｐＨ値が除々に上
昇して所定の値以上になればポンプγが駆動してイオン
交換塔８にめっき液が送られるようになる。As a result of continuing the operation in this state, when the pH value gradually increases and reaches a predetermined value or more, the pump γ is driven and the plating solution is sent to the ion exchange tower 8.
イオン交換塔８には塩酸と硫酸で再生された強酸性カチ
オン交換樹脂が装填され、めっき液を通したときの吸着
反応は次の通りである。The ion exchange column 8 is loaded with a strongly acidic cation exchange resin regenerated with hydrochloric acid and sulfuric acid, and the adsorption reaction when the plating solution is passed through it is as follows.
２（Ｒ８０３Ｈ）十ＮｌＳＯ４
→２（Ｒ−８０３）Ｎｊ＋Ｈ２ＳＯ４
２（ＲＳＯ３Ｈ） 十ＮＩＣＡ’２
→２ （Ｒ−８０３） Ｎｉ ＋ ２ ＨＣＩＪこの様
に硫酸ニッケルや塩化ニッケルの塩が吸着されて、硫酸
と塩酸が生成しめつき液のｐＨ値が低下するものである
。2 (R803H) 10 NlSO4 → 2 (R-803) Nj + H2SO4 2 (RSO3H) 10 NICA'2 → 2 (R-803) Ni + 2 HCIJ In this way, nickel sulfate and nickel chloride salts are adsorbed, and sulfuric acid and Hydrochloric acid is produced and the pH value of the tightening solution decreases.
イオン交換塔の操業方法は通常の方法で行われるが、そ
の規模によってはイオン交換塔を２基設置し各々交互に
カチオンの吸着と回収を行わせて常時運転することがで
きるが操業率の低い場合はイオン交換塔を１基のみ設置
して、めっき液が送られない間に回収反応を行うことも
可能である。Ion exchange towers are operated in the usual manner, but depending on the scale of the tower, two ion exchange towers can be installed and each one can alternately adsorb and recover cations, allowing constant operation, but the operating rate is low. In some cases, it is also possible to install only one ion exchange column and perform the recovery reaction while the plating solution is not being sent.
イオン交換樹脂が塩で飽和されると塩酸と硫酸を通じて
樹脂の再生が行われるがその時の反応は次の通りである
。When the ion exchange resin is saturated with salt, the resin is regenerated through hydrochloric acid and sulfuric acid, and the reaction at that time is as follows.
２ （ＲＳＯａ ） Ｎｔ ＋ Ｈ２ＳＯ４→２（Ｒ−
８０３−Ｈ）＋Ｎ１５Ｏ。2 (RSOa) Nt + H2SO4→2(R-
803-H)+N15O.
２ （Ｒ−ＳＯ３） Ｎｉ ＋２ＨＣＩＪ→２（ＲＳＯ
ｓ Ｈ） 十Ｎｔ Ｃ１１２この様に吸着されたニッ
ケルは硫酸ニッケルないし塩化ニッケルとして回収する
ことができるものである。2 (R-SO3) Ni +2HCIJ→2(RSO
s H) 10 Nt C112 The nickel thus adsorbed can be recovered as nickel sulfate or nickel chloride.
以上説明した如く本発明を実施することにより従来しば
しばめっき液のｐＨ値を測定し、その結果によって硫酸
及び塩酸を添加していたがその必要がなく、まためっき
液が結晶化するおそれもなくかつ漸増するニッケルイオ
ンを硫酸ニッケル及び塩化ニッケルとして回収できるも
のである。As explained above, by carrying out the present invention, there is no need for conventionally measuring the pH value of the plating solution and adding sulfuric acid and hydrochloric acid based on the results, and there is no fear that the plating solution will crystallize. The gradually increasing amount of nickel ions can be recovered as nickel sulfate and nickel chloride.
図面は本発明の実施例を模式図で示したものである。
１・・・・・・メッキ槽、３・・・・・・ｐＨ測定槽、
８・・・・・・イオン交換塔、２，７，１０・・・・・
・メッキ液循環用ポンプ。The drawings schematically show embodiments of the invention. 1... Plating tank, 3... pH measurement tank,
8...Ion exchange tower, 2,7,10...
・Pump for circulating plating solution.
Claims (1)
置備えたｐＨ値測測定槽カチオン交換樹脂を装填したイ
オン交換塔を設置し、めっき液のｐＨ値が所定の値より
高い場合に該めっき液を該イオン交換塔に循環させるこ
とによりめっき液のｐＨ値を調整する方法。1. In electrolytic nickel plating, an ion exchange tower loaded with a cation exchange resin is installed in a pH value measuring tank equipped with an automatic pH value measuring device, and when the pH value of the plating solution is higher than a predetermined value, the plating solution is A method of adjusting the pH value of a plating solution by circulating it through an ion exchange tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9436876A JPS5824519B2 (en) | 1976-08-06 | 1976-08-06 | How to adjust the pH of electrolytic nickel plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9436876A JPS5824519B2 (en) | 1976-08-06 | 1976-08-06 | How to adjust the pH of electrolytic nickel plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5319148A JPS5319148A (en) | 1978-02-22 |
| JPS5824519B2 true JPS5824519B2 (en) | 1983-05-21 |
Family
ID=14108364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9436876A Expired JPS5824519B2 (en) | 1976-08-06 | 1976-08-06 | How to adjust the pH of electrolytic nickel plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5824519B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665777A (en) * | 1992-08-24 | 1994-03-08 | Iketsukusu Kogyo:Kk | Production of porous forming die by electroforming |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4917709A (en) * | 1987-08-27 | 1990-04-17 | O. I. Corporation | Permeation pH control system |
| CN105217728A (en) * | 2015-10-12 | 2016-01-06 | 西南石油大学 | A kind of pH value of solution automatic control device based on ion exchange principle and using method thereof |
| GB2617690A (en) * | 2022-03-07 | 2023-10-18 | Enapter S R L | Electrolyte regeneration |
-
1976
- 1976-08-06 JP JP9436876A patent/JPS5824519B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665777A (en) * | 1992-08-24 | 1994-03-08 | Iketsukusu Kogyo:Kk | Production of porous forming die by electroforming |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5319148A (en) | 1978-02-22 |
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