JP2002322599A - Method for plating with trivalent chromium - Google Patents
Method for plating with trivalent chromiumInfo
- Publication number
- JP2002322599A JP2002322599A JP2001123790A JP2001123790A JP2002322599A JP 2002322599 A JP2002322599 A JP 2002322599A JP 2001123790 A JP2001123790 A JP 2001123790A JP 2001123790 A JP2001123790 A JP 2001123790A JP 2002322599 A JP2002322599 A JP 2002322599A
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- JP
- Japan
- Prior art keywords
- plating
- plating solution
- chromium
- ammonium chloride
- 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.)
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Abstract
Description
【０００１】（１） 産業上の利用分野 クロムめっきは装飾用および工業用として多くの産業分
野で使われている。クロムめっきは大気中で腐食せず光
沢を失わないために装飾用として広く使われると共に、
高い硬度と低い摩擦係数を有するために耐摩耗性を要す
る機械部品等に広く用いられている。しかしながら、こ
のめっきに使われるめっき液には多量の有害な６価クロ
ムが使われるために、毒性の少ないめっき液の開発が強
く望まれている。(1) Industrial application Chromium plating is used in many industrial fields for decorative and industrial purposes. Chrome plating is widely used for decorative purposes because it does not corrode in the atmosphere and does not lose its luster.
It is widely used for mechanical parts and the like that require wear resistance because of its high hardness and low coefficient of friction. However, since a large amount of harmful hexavalent chromium is used in the plating solution used for this plating, development of a plating solution with low toxicity is strongly desired.
【０００２】本発明のクロムめっきは毒性の少ない３価
クロムを用いるため、従来の自動車やオートバイ等の機
械部品や各種金型、印刷や圧延ロール等のクロムめっき
に利用が期待される。[0002] Since chromium plating of the present invention uses trivalent chromium with low toxicity, it is expected to be used for chrome plating of conventional machine parts such as automobiles and motorcycles, various molds, printing and rolling rolls.
【０００３】（２）従来の技術 これまでクロムめっきは６価クロムを含むサージェント
浴と呼ばれるめっき液やフッ化物や有機スルフォン酸を
含む６価クロム浴等により行なわれている。特公昭５７
−１１３９６及び特開昭５６−１１２４９３に記載され
ているように、３価クロム浴による装飾クロムめっきは
実用化されるようになったが、クロム酸を多量に使用す
る工業用クロムめっきの分野では浴寿命などに問題があ
り、工業用として使用できる３価クロム浴は未だに開発
されていない。(2) Prior Art Conventionally, chromium plating has been carried out using a plating solution called a surge bath containing hexavalent chromium, or a hexavalent chromium bath containing fluoride or organic sulfonic acid. Tokiko 57
As described in JP-A-11396 and JP-A-56-112493, decorative chromium plating using a trivalent chromium bath has come into practical use, but in the field of industrial chrome plating using a large amount of chromic acid. There is a problem in bath life and the like, and a trivalent chromium bath that can be used for industrial use has not yet been developed.
【０００４】（３） 本発明が解決しようとしている問
題点 上記のように、これまで３価クロムめっきに関して、実
用的なめっき液は開発されていない。本発明では従来の
クロムめっきに使われている有害な６価クロムを使わな
いクロムめっき法に関するものである。すなわち、クロ
ムめっき工場で働く従業員の健康を損なわないクロムめ
っき液を提供し、また、火災や地震、不慮の事故等によ
るめっき液の流失の際にも公害を引き起こす恐れがな
い、環境に優しいめっき液を提供しようとするものであ
る。(3) Problems to be solved by the present invention As described above, no practical plating solution has been developed for trivalent chromium plating. The present invention relates to a chromium plating method that does not use harmful hexavalent chromium used in conventional chromium plating. In other words, it provides a chrome plating solution that does not impair the health of employees working in a chrome plating factory, and is environmentally friendly because there is no danger of causing pollution in the event of a plating solution spill due to a fire, earthquake, or accident. It is intended to provide a plating solution.
【０００５】本発明のクロムめっきは毒性の少ない３価
クロムを用いるため、現在、毒性が問題となっている６
価クロムめっき浴の代替用のめっき液として、自動車や
オートバイ等の機械部品や各種金型、印刷や圧延ロール
等のクロムめっきに利用が期待される。Since the chromium plating of the present invention uses trivalent chromium having low toxicity, toxicity is a problem at present.
It is expected to be used as a plating solution as a substitute for a chromium plating bath for chrome plating of machine parts such as automobiles and motorcycles, various molds, printing and rolling rolls, and the like.
【０００６】（４）問題点を解決するための手段および
その効果 有害な６価クロムを使わないめっき液として３価クロム
浴は長い間研究されてきたが、めっきを行いながら長期
間めっき液の組成を一定に保つ事は困難であり、そのよ
うなめっき液組成やその管理法はこれまで確立されてい
ない。本発明ではこれらの点を解決したものである。(4) Means for Solving the Problems and Their Effects A trivalent chromium bath has been studied for a long time as a plating solution that does not use harmful hexavalent chromium. It is difficult to keep the composition constant, and such a plating solution composition and a management method thereof have not been established so far. The present invention has solved these points.
【０００７】本発明は、塩化クロム及び塩化アンモニウ
ムを含んで成るめっき液を用いて３価クロムめっきする
にあたり、めっき液の一部を冷却装置に循環させ、この
冷却装置において塩化アンモニウムの一部を晶析させ取
除くことにより、めっき液中の塩化アンモニウム濃度を
制御しながらめっきする、３価クロムめっき方法を提供
する。According to the present invention, in plating trivalent chromium using a plating solution containing chromium chloride and ammonium chloride, a part of the plating solution is circulated to a cooling device, and a part of the ammonium chloride is removed in the cooling device. Provided is a trivalent chromium plating method for performing plating while controlling the concentration of ammonium chloride in a plating solution by crystallization and removal.
【０００８】ここで、陰極におけるクロムの析出に伴う
めっき液中の塩素分の蓄積及び陽極における塩化アンモ
ニウム分解に伴う塩素分の蓄積とアンモニウム分の消耗
に応じて、めっき液に水酸化アンモニウムを添加しなが
らめっきすることにより、長時間連続運転が可能とな
る。Here, ammonium hydroxide is added to the plating solution in accordance with the accumulation of chlorine in the plating solution due to the deposition of chromium at the cathode and the accumulation of chlorine and the consumption of ammonium due to the decomposition of ammonium chloride at the anode. By performing plating while plating, continuous operation can be performed for a long time.
【０００９】陽極材料として炭素（カーボン）を使うこ
とが好ましいが、白金を使うことも可能である。It is preferable to use carbon as the anode material, but it is also possible to use platinum.
【００１０】めっき液として、さらにグリシンおよび
（または）硼酸および（または）塩化アルミニウムを含
むものを用いるのが好ましい。It is preferable to use a plating solution further containing glycine and / or boric acid and / or aluminum chloride.
【００１１】また、本発明は、めっき槽と、めっき液冷
却晶析槽と、両者を結ぶめっき液循環管路とを含んで成
る、３価クロムめっき装置を提供する。Further, the present invention provides a trivalent chromium plating apparatus including a plating tank, a plating solution cooling and crystallization tank, and a plating solution circulation pipe connecting the both.
【００１２】ここで、めっき液循環管路に、さらに熱交
換器および（または）フィルターおよび（または）加熱
器を組込むことが好ましい。Here, it is preferable to further incorporate a heat exchanger and / or a filter and / or a heater in the plating solution circulation pipeline.
【００１３】また、本発明は、塩化クロム及び塩化アン
モニウムを含んで成り、塩化アンモニウム含有量がめっ
き時のめっき液温度より低い温度で過飽和となり晶析す
る量である、めっき液組成物すなわちめっき浴を提供す
る。Further, the present invention provides a plating solution composition, that is, a plating bath, comprising chromium chloride and ammonium chloride, wherein the ammonium chloride content is an amount that becomes supersaturated and crystallizes at a temperature lower than the plating solution temperature during plating. I will provide a.
【００１４】本発明者は、塩化アンモニウムを多量に含
む３価クロム浴でカーボンを陽極としてめっきを行うと
陽極から多量の窒素ガスが発生し塩化アンモニウムが陽
極で分解することすることを実験的に見出した。本発明
はこれをきっかけとして成された。電解中に陽極で分解
消耗するアンモニウムイオンの量を水酸化アンモニウム
の添加により補充すると共に、めっきされる金属クロム
の補充のために添加する塩化クロムの塩素分も水酸化ア
ンモニウムの添加により塩化アンモニウムの形に替え、
めっき液を冷却することにより余分に生じた塩化アンモ
ニウムを晶析除去して、めっき液の組成を一定に保つこ
とができるのではないかと考え、これを実験により確認
した。The present inventor has experimentally confirmed that when plating is performed using carbon as an anode in a trivalent chromium bath containing a large amount of ammonium chloride, a large amount of nitrogen gas is generated from the anode and ammonium chloride is decomposed at the anode. I found it. The present invention has been made based on this. The amount of ammonium ions decomposed and consumed at the anode during electrolysis is supplemented by the addition of ammonium hydroxide, and the chlorine content of chromium chloride added to supplement the metal chromium to be plated is also reduced by the addition of ammonium hydroxide. Change to shape,
It was thought that it was possible to keep the composition of the plating solution constant by crystallizing and removing excess ammonium chloride generated by cooling the plating solution, and this was confirmed by experiments.
【００１５】この結果、めっき液の組成を長期間にわた
り一定に保つことが可能になり、硬質クロムのような厚
付け用のクロムめっきを可能とする３価クロムめっき方
法の開発に成功したのである。As a result, the composition of the plating solution can be kept constant over a long period of time, and a trivalent chromium plating method has been successfully developed which enables chromium plating for thick coating such as hard chromium. .
【００１６】なお、３価クロム浴中の塩化アンモニウム
の飽和溶解度は他の成分の含有量により異なるが、実験
の結果、塩化クロム300g/l、グリシン50g/l、硼酸30g/
l、を含む浴では塩化アンモニウムの飽和溶解量は240g/
lであり、塩化アルミニウムを50g/l、100g/l、150g/l、
および200g/l含有する３価クロムめっき浴の塩化アンモ
ニウムの飽和溶解量は200g/l、150g/l、100g/l、および
50g/lであった。The saturated solubility of ammonium chloride in the trivalent chromium bath varies depending on the content of other components. As a result of experiments, it was found that chromium chloride was 300 g / l, glycine was 50 g / l, and boric acid was 30 g / l.
l, the saturated dissolved amount of ammonium chloride is 240 g /
l, aluminum chloride 50g / l, 100g / l, 150g / l,
And 200 g / l containing trivalent chromium plating bath have saturated solubility of ammonium chloride of 200 g / l, 150 g / l, 100 g / l, and
It was 50 g / l.
【００１７】（５）実施例 以下に本発明の実施例を示し更に詳細に説明する。図１
は、本発明による３価クロムめっき装置の一例を示した
ものである。塩化クロム浴では電析した金属分の補給に
塩化クロムを用いるので、金属の析出に伴い液中に塩素
イオンが蓄積されることと、陽極で分解消耗するアンモ
ニア分を補給するために本実施例では水酸化アンモニウ
ムを添加する。このため、めっき液中に塩化アンモニウ
ムが蓄積することになる。この過剰の塩化アンモニウム
を除去するために図１の装置が必要となる。すなわち、
めっき槽１に入っている塩化アンモニウムの高濃度なめ
っき液はポンプ２により熱交換器３に送られ、ついで冷
却晶析槽４に入り液中の過剰な塩化アンモニウムを晶析
した後、フィルター５により晶析した塩化アンモニウム
を充分に除去し、ポンプ６と熱交換器３と加熱器７を通
ってめっき液温度まで加熱され、めっき槽１に戻る。ま
た、陽極で分解するアンモニアイオンや金属クロム分の
供給のため、補給液タンク８より水酸化アンモニウム、
グリシン、硼酸、塩化クロム等を含む補給液が定量ポン
プ９により供給される。(5) Embodiment An embodiment of the present invention will be described below and will be described in more detail. FIG.
1 shows an example of a trivalent chromium plating apparatus according to the present invention. In the chromium chloride bath, chromium chloride is used for replenishing the deposited metal. Then, ammonium hydroxide is added. Therefore, ammonium chloride accumulates in the plating solution. The apparatus of FIG. 1 is required to remove this excess ammonium chloride. That is,
The plating solution having a high concentration of ammonium chloride contained in the plating tank 1 is sent to the heat exchanger 3 by the pump 2 and then enters the cooling crystallization tank 4 where excess ammonium chloride in the solution is crystallized. The ammonium chloride crystallized by the above is sufficiently removed, heated to the plating solution temperature through the pump 6, the heat exchanger 3 and the heater 7, and returned to the plating bath 1. In order to supply ammonia ions and metal chromium which decompose at the anode, ammonium hydroxide,
A replenisher containing glycine, boric acid, chromium chloride and the like is supplied by the metering pump 9.
【００１８】実施例１ 図１の装置を用いて、次のめっき浴、すなわち、塩化ク
ロム300g/l、塩化アンモニウム150g/l、グリシン50g/
l、硼酸30g/l、塩化アルミニウム 50g/lを含む３価クロ
ムめっき浴により５０℃、４０Ａ/dm2 の条件で長時間
電解を行い、２万クーロン/L 通電するたびに水酸化ア
ンモニウム（２８％）を３．２ml/L、塩化クロム６水和
物０．４４ｇ/Lの割合で添加してクロムめっきを継続し
たところ１００万クーロンの通電でも良好なクロムめっ
きが得られた。この時のクロムめっきの電流効率は約２
０％とほぼ一定値を示した。この時の図１に示す装置に
おける冷却晶析槽内のめっき液の温度は２０℃であっ
た。Example 1 Using the apparatus of FIG. 1, the following plating baths were used: chromium chloride 300 g / l, ammonium chloride 150 g / l, glycine 50 g / l.
, 30 g / l of boric acid and 50 g / l of aluminum chloride in a trivalent chromium plating bath at 50 ° C and 40 A / dm 2 for a long time, and 20,000 coulombs / L of ammonium hydroxide (28 %) Was added at a rate of 3.2 ml / L and chromium chloride hexahydrate at a rate of 0.44 g / L, and chromium plating was continued. As a result, good chromium plating was obtained even with a current of 1 million coulombs. The current efficiency of the chrome plating at this time is about 2
The value was almost constant at 0%. At this time, the temperature of the plating solution in the cooling crystallization tank in the apparatus shown in FIG. 1 was 20 ° C.
【００１９】なお、この浴で水酸化アンモニウムを添加
せずにめっきを続けると約１０万クーロンでめっきが付
かなくなった。When plating was continued in this bath without adding ammonium hydroxide, plating stopped at about 100,000 coulombs.
【００２０】実施例２ 図１の装置と次のような３価クロムめっき液（塩化クロ
ム300g/l、塩化アンモニウム150g/l、グリシン50g/l、
硼酸30g/l）を用いて、電流密度４０Ａ/dm2、めっき液
の温度５０℃、冷却晶析槽の温度１０℃とし、めっき電
流の通電量1万クーロン毎にめっき液１リットル当たり
アンモニア水（２８％）を3.2ｍｌ/L、塩化クロム６水
和物０．２２ｇ/L、グリシン０．１４ｇ/L、硼酸０．０
３６ｇ/Lを添加しながら連続してクロムめっきを行なっ
たところ２００万クーロン/Lを過ぎてもめっきが可能で
あった。Example 2 A trivalent chromium plating solution (chromium chloride 300 g / l, ammonium chloride 150 g / l, glycine 50 g / l,
Using boric acid (30 g / l), the current density was 40 A / dm 2 , the temperature of the plating solution was 50 ° C., the temperature of the cooling crystallization tank was 10 ° C., and every 10,000 coulombs of plating current, ammonia water per liter of plating solution was used. (28%) in 3.2 ml / L, chromium chloride hexahydrate 0.22 g / L, glycine 0.14 g / L, boric acid 0.0
When chromium plating was continuously performed while adding 36 g / L, plating was possible even after 2 million coulombs / L.
【００２１】実施例３ 図１の装置で電極として、炭素電極に代えて、白金を被
覆したチタン電極を用いて、実施例１の条件、すなわ
ち、塩化クロム300g/l、塩化アンモニウム150g/l、グリ
シン50g/l、硼酸30g/l、塩化アルミニウム 50g/lを含む
３価クロムめっき浴により５０℃、４０Ａ/dm2 の条件
で長時間電解を行い良好なクロムめっきを得た。Example 3 In the apparatus of FIG. 1, instead of the carbon electrode, a titanium electrode coated with platinum was used instead of the carbon electrode, and the conditions of Example 1, namely, chromium chloride 300 g / l, ammonium chloride 150 g / l, Electrolysis was carried out for a long time at 50 ° C. and 40 A / dm 2 in a trivalent chromium plating bath containing 50 g / l of glycine, 30 g / l of boric acid and 50 g / l of aluminum chloride to obtain good chromium plating.
【図１】本発明方法を実施するためのめっき装置を示す
線図的説明図である。FIG. 1 is a schematic explanatory view showing a plating apparatus for carrying out a method of the present invention.
１ めっき槽 ２ ポンプ ３ 熱交換器 ４ 冷却晶析槽 ５ フィルター ６ ポンプ ７ 加熱器 ８ 補給液タンク ９ ポンプ DESCRIPTION OF SYMBOLS 1 Plating tank 2 Pump 3 Heat exchanger 4 Cooling and crystallization tank 5 Filter 6 Pump 7 Heater 8 Replenisher tank 9 Pump
───────────────────────────────────────────────────── 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） Ｃ２５Ｄ 21/18 Ｃ２５Ｄ 21/18 Ｇ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C25D 21/18 C25D 21/18 G
Claims (10)
んで成るめっき液を用いて３価クロムめっきするにあた
り、めっき液の一部を冷却装置に循環させ、この冷却装
置において塩化アンモニウムの一部を晶析させ取除くこ
とにより、めっき液中の塩化アンモニウム濃度を制御し
ながらめっきする、３価クロムめっき方法。When plating trivalent chromium using a plating solution containing chromium chloride and ammonium chloride, a part of the plating solution is circulated to a cooling device, and a part of the ammonium chloride is crystallized in the cooling device. A trivalent chromium plating method in which plating is performed while controlling the concentration of ammonium chloride in the plating solution by removing and removing the plating solution.
液中の塩素分の蓄積および陽極における塩化アンモニウ
ムの分解に伴う塩素分の蓄積とアンモニウム分の消耗に
応じて、めっき液に水酸化アンモニウムを添加しながら
めっきする、請求項１に記載の方法。2. An ammonium hydroxide is added to the plating solution according to the accumulation of chlorine in the plating solution due to the deposition of chromium at the cathode and the accumulation of chlorine and the consumption of ammonium due to the decomposition of ammonium chloride at the anode. The method according to claim 1, wherein the plating is performed while plating.
白金を使う、請求項２に記載の方法。3. The method according to claim 2, wherein carbon (carbon) or platinum is used as the anode material.
ものを用いる、請求項１〜３のいずれかに記載の方法。4. The method according to claim 1, wherein a plating solution further containing glycine is used.
を用いる、請求項１〜４のいずれかに記載の方法。5. The method according to claim 1, wherein a plating solution further containing boric acid is used.
ムを含むものを使う、請求項１〜５のいずれかに記載の
方法。6. The method according to claim 1, wherein a plating solution further containing aluminum chloride is used.
者を結ぶめっき液循環管路とを含んで成る、請求項１に
記載の方法を実施するための３価クロムめっき装置。7. A trivalent chromium plating apparatus for carrying out the method according to claim 1, comprising a plating tank, a plating solution cooling and crystallization tank, and a plating solution circulation line connecting the two.
組込んだ、請求項７に記載のめっき装置。8. The plating apparatus according to claim 7, wherein a heat exchanger is further incorporated in the plating solution circulation pipeline.
および加熱器を組込んだ、請求項８に記載のめっき装
置。9. The plating apparatus according to claim 8, wherein a filter and a heater are further incorporated in the plating solution circulation pipeline.
含んで成り、塩化アンモニウム含有量がめっき時のめっ
き液温度より低い温度で過飽和となり晶析する量であ
る、請求項１に記載の方法を実施するためのめっき液組
成物。10. The method according to claim 1, comprising chromium chloride and ammonium chloride, wherein the ammonium chloride content is an amount that becomes supersaturated and crystallizes at a temperature lower than the plating solution temperature during plating. Plating solution composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001123790A JP2002322599A (en) | 2001-04-23 | 2001-04-23 | Method for plating with trivalent chromium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001123790A JP2002322599A (en) | 2001-04-23 | 2001-04-23 | Method for plating with trivalent chromium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002322599A true JP2002322599A (en) | 2002-11-08 |
Family
ID=18973281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001123790A Pending JP2002322599A (en) | 2001-04-23 | 2001-04-23 | Method for plating with trivalent chromium |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006249518A (en) * | 2005-03-11 | 2006-09-21 | Koka Chrom Kogyo Kk | Method for supplying chromium ion to trivalent chromium plating bath |
| JP2009249707A (en) * | 2008-04-09 | 2009-10-29 | Shigeo Hoshino | Trivalent chromium-plating liquid management device |
| WO2010026886A1 (en) | 2008-09-05 | 2010-03-11 | 日本化学工業株式会社 | Process for production of chromium hydroxide |
| WO2010026915A1 (en) | 2008-09-05 | 2010-03-11 | 日本化学工業株式会社 | Chromium(iii) carbonate and process for production of same |
| WO2010026884A1 (en) * | 2008-09-05 | 2010-03-11 | 日本化学工業株式会社 | Method for producing aqueous solution containing chromium (iii) source |
| JP4764886B2 (en) * | 2004-12-20 | 2011-09-07 | アトテック・ドイチュラント・ゲーエムベーハー | Continuous operation of acidic or alkaline zinc or zinc alloy bath |
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| JP4764886B2 (en) * | 2004-12-20 | 2011-09-07 | アトテック・ドイチュラント・ゲーエムベーハー | Continuous operation of acidic or alkaline zinc or zinc alloy bath |
| JP4667084B2 (en) * | 2005-03-11 | 2011-04-06 | 硬化クローム工業株式会社 | Chromium ion replenishment method for trivalent chromium plating bath |
| JP2006249518A (en) * | 2005-03-11 | 2006-09-21 | Koka Chrom Kogyo Kk | Method for supplying chromium ion to trivalent chromium plating bath |
| JP2009249707A (en) * | 2008-04-09 | 2009-10-29 | Shigeo Hoshino | Trivalent chromium-plating liquid management device |
| WO2010026915A1 (en) | 2008-09-05 | 2010-03-11 | 日本化学工業株式会社 | Chromium(iii) carbonate and process for production of same |
| WO2010026884A1 (en) * | 2008-09-05 | 2010-03-11 | 日本化学工業株式会社 | Method for producing aqueous solution containing chromium (iii) source |
| WO2010026886A1 (en) | 2008-09-05 | 2010-03-11 | 日本化学工業株式会社 | Process for production of chromium hydroxide |
| JPWO2010026886A1 (en) * | 2008-09-05 | 2012-02-02 | 日本化学工業株式会社 | Method for producing chromium hydroxide |
| JPWO2010026884A1 (en) * | 2008-09-05 | 2012-02-02 | 日本化学工業株式会社 | Method for producing an aqueous solution containing a chromium (III) source |
| JP2011184734A (en) * | 2010-03-08 | 2011-09-22 | Electroplating Eng Of Japan Co | Gold plating method using sulfite gold plating liquid |
| JP2015067849A (en) * | 2013-09-27 | 2015-04-13 | 豊田合成株式会社 | Regeneration apparatus for trivalent chromium plating solution, trivalent chromium plating system with the regeneration apparatus, and regeneration method of trivalent chromium solution |
| CN104213180A (en) * | 2014-09-17 | 2014-12-17 | 丹阳市新光电子有限公司 | Electroplating liquid circulating system of flexible circuit board |
| CN104213180B (en) * | 2014-09-17 | 2016-06-08 | 丹阳市新光电子有限公司 | Flexible PCB electroplate liquid blood circulation |
| KR101676246B1 (en) | 2015-04-20 | 2016-11-30 | 현대자동차주식회사 | The Materials of Auxiliary Anode using Trivalent Chromium Plating and The method of Plating used by Auxiliary Anode |
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