JPH01275799A - Method for feeding zn ion in galvanizing - Google Patents
Method for feeding zn ion in galvanizingInfo
- Publication number
- JPH01275799A JPH01275799A JP10389588A JP10389588A JPH01275799A JP H01275799 A JPH01275799 A JP H01275799A JP 10389588 A JP10389588 A JP 10389588A JP 10389588 A JP10389588 A JP 10389588A JP H01275799 A JPH01275799 A JP H01275799A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- galvanizing
- soln
- ions
- plating solution
- 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
- 238000000034 method Methods 0.000 title claims description 9
- 238000005246 galvanizing Methods 0.000 title abstract 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 238000007747 plating Methods 0.000 claims description 31
- 238000004090 dissolution Methods 0.000 abstract description 15
- 239000000843 powder Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000004744 fabric Substances 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052737 gold Inorganic materials 0.000 abstract description 2
- 229910052738 indium Inorganic materials 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Automation & Control Theory (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野） ・
本発明は電気Ｚｎメッキ、特に不溶性電極を用いる電気
ＺｎメッキにおけるＺｎイオンの供給方法に関するもの
でおる。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) - The present invention relates to a method for supplying Zn ions in electrolytic Zn plating, particularly in electrolytic Zn plating using an insoluble electrode.
不溶性陽極を用いた電気Ｚｎメッキは、一般に硫酸塩浴
が用いられ、陰極反応及び陽極反応は、
陰極反応 Ｚｎ２”十′２ｅ−→Ｚｎ・・・・・・・・
（１）陽極反応 ＳＯ４”−＋Ｈ２０→
ＨｚＳＯ＋＋ＨＯｚ＋２８− ・・・・（２）であり、
陰極では（１）式のようにＺｎの析出によりメッキ液中
のＺｎイオンの減少が起り、陽極では（２）式のように
ｐＨの低下が起るため、Ｚｎイオンの補給とメッキ液の
ｐＨ調整が必要である。即ち硫酸塩を主としたＺｎメッ
キ液中で不溶性陽極を用いて電気メッキを行う場合、金
属ＺｎをＺｎイオンの補給に用いるとＺ ｒｌ ＋Ｈｚ
ＳＯ４−＋ Ｚ ｎ ３Ｑ４＋ｌ（２・・−・−・・・
・（３）の反応が生じ、上記（１）式のＺｎイオンの供
給と、（２）式のメッキ液ｐＨの低下と（３）式のｐＨ
上昇がバランスし、メッキ液１）Ｈが一定に維持される
利点がある。In electrolytic Zn plating using an insoluble anode, a sulfate bath is generally used, and the cathodic reaction and anodic reaction are as follows:
(1) Anodic reaction SO4”-+H20→ HzSO++HOz+28- (2),
At the cathode, the Zn ions in the plating solution decrease as shown in equation (1), and at the anode, the pH decreases as shown in equation (2). Adjustments are required. That is, when electroplating is performed using an insoluble anode in a Zn plating solution mainly containing sulfate, if metallic Zn is used to replenish Zn ions, Z rl +Hz
SO4−+ Z n 3Q4+l(2・・−・−・・・
- The reaction (3) occurs, supplying Zn ions in the above equation (1), decreasing the pH of the plating solution in the equation (2), and decreasing the pH in the equation (3).
There is an advantage that the increase is balanced and the plating solution 1)H is maintained constant.
Ｚｎイオンの供給源として金属Ｚｎ粉末またはＺｎｏ、
Ｚｎ （Ｏｆ−！ｚ）、ＺｎＣＯ３等の金属塩粉末をメ
ッキ液に溶解させ、Ｚｎイオンを補給する方法が、特公
昭６０’−１８５９８号公報等に開示されている。また
金属Ｚｎを溶解するのに、金属ＺｎにＺｎより員な金属
を合金化させ、Ｚｎの溶解速度を向上させる方法が特開
昭６２−２４３７９８号公報に開示されている。Metallic Zn powder or Zno as a source of Zn ions,
A method of replenishing Zn ions by dissolving metal salt powder such as Zn (Of-!z) or ZnCO3 in a plating solution is disclosed in Japanese Patent Publication No. 18598/1986. Furthermore, Japanese Patent Laid-Open No. 62-243798 discloses a method of alloying metal Zn with a metal more powerful than Zn to improve the dissolution rate of Zn.
（発明が解決しようとする課題〕
しかしながら硫駿塩を主体としたＺｎメッキ浴中では、
金属Ｚｎの溶解に伴い、メッキ液のＤＨが上昇し、金属
Ｚｎの表面に生成する水酸化物の皮膜を形成し、金属Ｚ
ｎの溶解速度が著しく減少する。また金属塩粉末は金属
Ｚｎに比べて溶解速度は極めて大きいが、コスト高とな
り、ハンドリング作業設備費も高価なものとなる。(Problem to be solved by the invention) However, in a Zn plating bath mainly containing sulfur salt,
As metal Zn dissolves, the DH of the plating solution increases, forming a hydroxide film on the surface of metal Zn, and dissolving metal Zn.
The dissolution rate of n is significantly reduced. Furthermore, although the dissolution rate of metal salt powder is much higher than that of metal Zn, the cost is high, and the cost of handling equipment is also high.
更に金属ＺｎにＺｎより貞な金属を合金化させたもので
は、合金化のためコストアップとなる事や、溶解後のＺ
ｎより真な金属の粉の除去に必要なハンドリング作業設
備費も高価なものとなり、メッキ液への粉の混入による
Ｚｎ被膜の特性劣化等の問題があり、実用的でない。Furthermore, when metal Zn is alloyed with a metal that is more pure than Zn, the cost increases due to alloying, and the Zn after melting increases.
The cost of the handling equipment required to remove the true metal powder is also high, and there are problems such as deterioration of the characteristics of the Zn coating due to the powder mixed into the plating solution, making it impractical.
一般に金属Ｚｎの溶解速度を大きくするためには、（イ
）金属Ｚｎの化学的溶解（腐食）条件を厳しくする。（
ロ）金属Ｚｎの表面積を大きくする等の手段があげられ
る。（イ）の具体策としてメッキ液のｐＨを下げ、温度
を上げ、液流速を上げ、更にＺｎイオン濃度を下げる。Generally, in order to increase the dissolution rate of metal Zn, (a) chemical dissolution (corrosion) conditions for metal Zn are made stricter. (
(b) Measures such as increasing the surface area of metal Zn can be cited. Specific measures for (a) include lowering the pH of the plating solution, increasing the temperature, increasing the solution flow rate, and further lowering the Zn ion concentration.
（ロ）の具体策としてメッキ液への被接触金属Ｚｎ量を
多くし、金属Ｚｎ塊を粉砕して微細化する等があり、そ
れぞれその効果を上げている。Specific measures for (b) include increasing the amount of metal Zn in contact with the plating solution and pulverizing metal Zn lumps to make them finer, each of which has been effective.
しかしこれ等の対策、手段には前述した電気メッキ液の
本質的な問題及び金属Ｚｎ溶解設備の大型化などにより
、工業的には制約がおり、夫本的な解決策とはなり得な
い。However, these countermeasures and means have industrial limitations due to the above-mentioned inherent problems with the electroplating solution and the increase in the size of metal Zn melting equipment, and cannot serve as practical solutions.
本発明はこれに鑑み、種々検討の結果、電気Ｚｎメッキ
におけるＺｎイオンの供給方法を開発したもので、不溶
性陽極を用いる電気Ｚｎメッキにおいて、Ｚｎ濃度の減
少したメッキ液に金属Ｚｎと金属Ｚｎより電位が貴な金
属を接触させて浸漬する事を特徴とするものである。In view of this, and as a result of various studies, the present invention has developed a method for supplying Zn ions in electrolytic Zn plating. It is characterized by contacting and immersing a metal with a noble potential.
本発明は、不溶性＠極を用いる電気Ｚｎメツ主において
、Ｚｎイオン濃度の減少したメッキ液に、Ｚｎイオンの
供給源として金属Ｚｎを溶解させる場合に、金属Ｚｎに
メッキ液中での電位がＺｎより肖な金属と接触させて浸
漬することにより、低コストにて金属Ｚｎの溶解速度を
従来技術に比へて著しく大きくし、陰極に析出するｌｎ
に相当する金属Ｚｎの溶解ｆｆ１（Ｚｎイオンの補給量
）を得てＺｎメッキ液中のＺｎイオン濃度をバランスさ
せることができる。The present invention provides an electric Zn method using an insoluble @electrode, in which when metallic Zn is dissolved as a supply source of Zn ions in a plating solution with a reduced Zn ion concentration, the electrical potential in the plating solution is By contacting and immersing the Zn metal in contact with a more suitable metal, the dissolution rate of Zn metal is significantly increased compared to the conventional technology at a low cost, and the ln precipitated on the cathode is
The Zn ion concentration in the Zn plating solution can be balanced by obtaining the dissolution ff1 (replenishment amount of Zn ions) of metal Zn corresponding to .
本発明に用いる金属Ｚｎは、−船釣な金属Ｚｎ（電気Ｚ
ｎ）でよく、その形状は塊、板。The metal Zn used in the present invention is - boat metal Zn (electric Zn)
n) and its shape is a lump or a plate.
小片１粒、粉末等のいずれの形状でも用いられ、特に限
定するものではないが前記の如く、メッキ液への被接触
面積を大きくするため、微細化することは溶解速度を上
げる方法として有効である。It can be used in any form, such as a single small piece or powder, and as mentioned above, miniaturization is an effective way to increase the dissolution rate in order to increase the area that comes into contact with the plating solution, although it is not particularly limited. be.
本発明における金属Ｚｎとの接触金属としては、メッキ
液中での電位がＺｎより貴な金属でおれば良く、例えば
Ｐｔ、Ａｕ、Ａｇ、Ｐｄ。The metal in contact with metal Zn in the present invention may be any metal whose potential in the plating solution is nobler than that of Zn, such as Pt, Au, Ag, and Pd.
Ｉｎ、Ｎｂ、Ｆｅ、Ｃｒ、Ｍｏ、Ｎ ｉ、Ｃｄ。In, Nb, Fe, Cr, Mo, Ni, Cd.
Ｃｏ、３ｎ等がある。尚本発明におけるＺｎより貴な金
属として、上記金属の外にＣｕ、ｐｂ。There are Co, 3n, etc. In addition to the above-mentioned metals, metals nobler than Zn in the present invention include Cu and pb.
３ｒ等が必るが、Ｚｎメッキ液中に溶解し、Ｚｎメッキ
皮膜中に共析して耐食性、メッキ密着性等に悪影響を及
ぼすようなものは望ましくない。また金属単体ではなく
合金、例えばＡｕ−Ａ９合金、Ｐｔ−Ｐｄ合金等でもよ
い。3r or the like is necessary, but it is not desirable to use a material that dissolves in the Zn plating solution and eutectoids into the Zn plating film and adversely affects corrosion resistance, plating adhesion, etc. Further, instead of a single metal, an alloy such as an Au-A9 alloy or a Pt-Pd alloy may be used.
次に本発明を実施例に基づいて詳細に説明する。Next, the present invention will be explained in detail based on examples.
第１図に示すようにＺｎメッキ槽（図示せず）に塩化ビ
ニールで形成したＺｎ溶解槽（１）を取付け、メッキ液
（２）を循環ポンプ（図示せず）により矢印方向に強制
循環した。Ｚｎ溶解槽（１）は図に示すように溶解槽（
１）内にろ布（３）と金属ネット（４）を配置し、金属
ネット（４）内に金属Ｚ ｎ （５）と金属棒（６）を
接触させて挿入した。As shown in Figure 1, a Zn dissolving tank (1) made of vinyl chloride was attached to a Zn plating tank (not shown), and the plating solution (2) was forcibly circulated in the direction of the arrow by a circulation pump (not shown). . The Zn dissolution tank (1) is a dissolution tank (1) as shown in the figure.
1) A filter cloth (3) and a metal net (4) were placed inside the chamber, and a metal Z n (5) and a metal rod (6) were inserted into the metal net (4) in contact with each other.
このようにしてＺｎメッキ液として
Ｚ ｎ ３０４ ・７Ｈ２０２５０ｇ／ ｌＮａＳＯ４
７０ｇ／ｌ
の組成のものを、ｐＨ＝１．０となるようにＨ２Ｓ Ｃ
）＋で調整し、液温５５°Ｃとして強制循環させた。金
属Ｚｎとしては通常の電気Ｚｎ（ｉＡ度９９、９９％以
上）を直径２＃の粒状に加工したものを用いた。金属ネ
ットと金属棒には金属Ｚｎより真な同一の金属又は合金
を用いた。In this way, Zn 304 7H20250g/lNaSO4 was used as Zn plating solution.
The composition of 70g/l was added to H2S C so that pH=1.0.
)+, and forced circulation was carried out at a liquid temperature of 55°C. As the metal Zn, ordinary electric Zn (iA degree 99, 99% or more) processed into particles with a diameter of 2# was used. The metal net and the metal rod were made of the same metal or alloy, which is truer than metal Zn.
このようにして金属ネットと金属棒に第１表に示す金属
Ｚｎより真な金属又は合金を用い金属Ｚｎの溶解速度を
求めた。その結果を金属ネットと金属棒のかわりに塩化
ビニールを用いた従来方法と比較して第１表に併記した
。In this way, the dissolution rate of metal Zn was determined using metals or alloys truer than metal Zn shown in Table 1 for the metal net and metal rod. The results are also listed in Table 1 in comparison with the conventional method using vinyl chloride instead of the metal net and metal rod.
金属Ｚｎの溶解速度は金属Ｚ ｎ １ Ｋ３の１時間あ
たりの溶解量で表わした。The dissolution rate of metal Zn was expressed as the amount of metal Z n 1 K3 dissolved per hour.
第１表
第１表から明らかなように、金属Ｚｎ粒のみからなる従
来方法では、Ｚｎの溶解速度が５Ｃｉ／に’ｊ・ｈｒと
著しく低いのに対し、本発明方法によれば１５０９／に
’ｊ・ｈｒ以上とＺｎの溶解速度が著しく大きいことが
判る。Table 1 As is clear from Table 1, in the conventional method consisting only of metallic Zn grains, the dissolution rate of Zn was extremely low at 5 Ci/'j·hr, whereas in the method of the present invention, it was 1509/hr. It can be seen that the dissolution rate of Zn is extremely high above 'j·hr.
てのように本発明方法によれば、Ｚｎｓ度の減少したＺ
ｎメッキ液にＺｎイオンを速やかに補給し、Ｚｔｌ１度
を上げることができ、メッキ液の通液量を電解で消費さ
れるＺｎ量に合わせることで所定のＺｎ′ａ度を保持す
ることができる等工業上顕著な効果を秦するものである
。According to the method of the present invention, Z
By quickly replenishing Zn ions to the n plating solution, the Ztl can be raised by 1 degree, and by matching the amount of plating solution passed to the amount of Zn consumed in electrolysis, the predetermined Zn'a degree can be maintained. It has a remarkable industrial effect.
第１図は本発明のＺｎ溶解槽の一実施例を示す説明図で
ある。
１．２ｎ溶解槽
２、メッキ液
３、ろ布
４、金属ネット
５、金属Ｚｎ
６、金属棒
第１図FIG. 1 is an explanatory diagram showing an embodiment of the Zn dissolving tank of the present invention. 1.2n dissolving tank 2, plating solution 3, filter cloth 4, metal net 5, metal Zn 6, metal rod Figure 1
Claims (1)
ｎ濃度の減少したメッキ液に金属Ｚｎと金属Ｚｎより電
位が貴な金属を接触させて浸漬する事を特徴とする電気
ＺｎメッキにおけるＺｎイオンの供給方法。(1) In electrolytic Zn plating using an insoluble anode, Z
A method for supplying Zn ions in electrolytic Zn plating, which comprises contacting and immersing metal Zn and a metal with a nobler potential than metal Zn in a plating solution with a reduced n concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10389588A JPH01275799A (en) | 1988-04-28 | 1988-04-28 | Method for feeding zn ion in galvanizing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10389588A JPH01275799A (en) | 1988-04-28 | 1988-04-28 | Method for feeding zn ion in galvanizing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01275799A true JPH01275799A (en) | 1989-11-06 |
Family
ID=14366159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10389588A Pending JPH01275799A (en) | 1988-04-28 | 1988-04-28 | Method for feeding zn ion in galvanizing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01275799A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739995B1 (en) * | 1992-09-16 | 1998-08-19 | Nippon Mining & Metals Co., Ltd. | Use of a Zn-Ni alloy for preparation of Zn-Ni alloy hot-dip galvanizing bath |
| JP2002206199A (en) * | 2000-12-28 | 2002-07-26 | Atotech Japan Kk | Copper dissolution tank in copper plating apparatus |
-
1988
- 1988-04-28 JP JP10389588A patent/JPH01275799A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739995B1 (en) * | 1992-09-16 | 1998-08-19 | Nippon Mining & Metals Co., Ltd. | Use of a Zn-Ni alloy for preparation of Zn-Ni alloy hot-dip galvanizing bath |
| JP2002206199A (en) * | 2000-12-28 | 2002-07-26 | Atotech Japan Kk | Copper dissolution tank in copper plating apparatus |
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