JP2860916B2 - Zinc-iron group metal alloy plating solution and zinc-iron group metal alloy plating method using the same - Google Patents
Zinc-iron group metal alloy plating solution and zinc-iron group metal alloy plating method using the sameInfo
- Publication number
- JP2860916B2 JP2860916B2 JP17542390A JP17542390A JP2860916B2 JP 2860916 B2 JP2860916 B2 JP 2860916B2 JP 17542390 A JP17542390 A JP 17542390A JP 17542390 A JP17542390 A JP 17542390A JP 2860916 B2 JP2860916 B2 JP 2860916B2
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- Prior art keywords
- zinc
- iron group
- group metal
- alloy plating
- metal alloy
- 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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- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は機能材料の１つとして有用な亜鉛−鉄族金属
合金膜を得ることのできるめっき液とそれを用いた湿式
めっき法に関する。Description: TECHNICAL FIELD The present invention relates to a plating solution capable of obtaining a zinc-iron group metal alloy film useful as one of the functional materials, and a wet plating method using the same.
（従来の技術） 自動車のボディーに電気めっきトタンの使用が一般化
し，自動車ボディーの耐食性の向上に役立っている。更
に，近年この耐食性を向上させる目的で亜鉛に鉄族金属
を含有させた亜鉛−鉄族金属合金電気めっきが，その優
れた特性により，高耐食性自動車用鋼板の表面処理とし
て広く工業化されている。(Prior Art) The use of electroplated tin in automobile bodies has become common, which has helped to improve the corrosion resistance of automobile bodies. Further, in recent years, zinc-iron group metal alloy electroplating in which zinc contains an iron group metal for the purpose of improving the corrosion resistance has been widely industrialized as a surface treatment of a high corrosion resistant automotive steel sheet due to its excellent properties.
現在，この種の合金めっきは水溶液を溶媒とした水溶
液電解法により，亜鉛−鉄族合金めっきを得ている。At present, in this type of alloy plating, zinc-iron group alloy plating is obtained by an aqueous solution electrolysis method using an aqueous solution as a solvent.
（発明が解決しようとする課題） これら，従来法による水溶液を溶媒とした水溶液電解
法による亜鉛−鉄族金属合金のめっき方法においては，
本系金属合金電析が電気化学的に卑な金属である亜鉛
が，より貴な金属である鉄族金属に比べて優先析出する
という特異性を有している。(Problems to be Solved by the Invention) In these conventional methods for plating a zinc-iron group metal alloy by an aqueous solution electrolysis method using an aqueous solution as a solvent,
This alloy has a peculiarity in that zinc, which is an electrochemically noble metal, is preferentially deposited compared to iron group metals, which are more noble metals.
そのため，めっき浴中の金属イオン組成と析出合金組
成が異なり，目的の析出合金組成の制御が容易ではな
く，めっき浴中の金属イオン組成の管理が難易であっ
た。この亜鉛−鉄族金属合金電析における異常性出現の
原因については，いくつかの諸説があるが，また実証さ
れるには至っていない。For this reason, the composition of the metal ion in the plating bath and the composition of the precipitated alloy were different, and it was not easy to control the composition of the target precipitated alloy, and it was difficult to control the composition of the metal ion in the plating bath. There are several theories about the cause of the appearance of anomalies in the zinc-iron group metal alloy electrodeposition, but they have not been proved.
そこで，本発明の技術的課題は，析出合金組成の制御
を容易にし，簡便な方法でめっき浴の管理が簡便な亜鉛
−鉄族金属合金のめっき液とそれを用いためっき方法を
提供することにある。Therefore, a technical problem of the present invention is to provide a plating solution of a zinc-iron group metal alloy and a plating method using the same, in which the composition of the deposited alloy is easily controlled and the plating bath is easily controlled by a simple method. It is in.
（課題を解決するための手段） 本発明によれば，亜鉛金属塩と鉄族金属塩とを溶媒に
溶かしためっき液において，前記溶媒は有機溶媒である
ことを特徴とする亜鉛−鉄族金属合金めっき液が得られ
る。(Means for Solving the Problems) According to the present invention, in a plating solution obtained by dissolving a zinc metal salt and an iron group metal salt in a solvent, the solvent is an organic solvent, wherein the zinc-iron group metal is used. An alloy plating solution is obtained.
本発明によれば、前記亜鉛−鉄族金属合金のめっき液
において，前記亜鉛金属塩，および前記鉄族金属塩が共
に塩化物であることを特徴とする亜鉛−鉄族金属合金め
っき液が得られる。According to the present invention, there is provided a zinc-iron group metal alloy plating solution, wherein the zinc metal salt and the iron group metal salt are both chlorides in the zinc-iron group metal alloy plating solution. Can be
本発明によれば、前記亜鉛−鉄族金属合金めっき液に
おいて，前記有機溶媒は誘電率が10以上の値を有するこ
とを特徴とする亜鉛−鉄族金属合金めっき液が得られ
る。According to the present invention, there is obtained a zinc-iron group metal alloy plating solution, wherein the organic solvent has a dielectric constant of 10 or more in the zinc-iron group metal alloy plating solution.
本発明によれば，前記亜鉛−鉄族金属合金めっき液に
おいて，前記めっき液は支持塩として過塩素酸塩類を含
むことを特徴とする亜鉛−鉄族金属合金めっき液が得ら
れる。According to the present invention, there is obtained a zinc-iron group metal alloy plating solution, wherein the plating solution contains perchlorates as a supporting salt in the zinc-iron group metal alloy plating solution.
本発明によれば，前記したいずれかの亜鉛−鉄族金属
合金めっき液を用いて，基板上に亜鉛−鉄族合金めっき
膜を電着させる方法において，前記溶媒は有機溶媒であ
ることを特徴とする亜鉛−鉄族金属合金めっき方法が得
られる。According to the present invention, in the method of electrodepositing a zinc-iron group alloy plating film on a substrate using any one of the above-described zinc-iron group metal alloy plating solutions, the solvent is an organic solvent. Is obtained.
ここで，本発明において使用される金属塩としての亜
鉛金属塩，および鉄族金属塩は，それぞれの金属の塩酸
塩，硫酸塩，硝酸塩等各種が使用できる。しかし，一般
に金属を非水溶媒系のめっき浴から電析させる場合に
は，水分の混入は好ましくなく，かつ後述するようにめ
っき浴中の水分が亜鉛−鉄族金属合金めっきにおけるめ
っき浴中に存在することが，めっき浴中の金属イオン組
成に対する析出合金組成が異なるという電気化学的に卑
な金属の優先析出する異常型析出を示すと考えられるこ
とから，水分を含んだめっき浴からは，目的のめっき膜
を得ることは容易ではない。Here, as the zinc metal salt and the iron group metal salt as the metal salt used in the present invention, various kinds such as hydrochloride, sulfate, nitrate of each metal can be used. However, in general, when a metal is electrodeposited from a non-aqueous solvent-based plating bath, it is not preferable to mix water, and as described later, the water in the plating bath may not be included in the plating bath in the zinc-iron group metal alloy plating. It is considered that the presence of the alloy indicates an abnormal type of precipitation in which the electrochemically base metal is preferentially deposited, in which the composition of the deposited alloy is different from the composition of the metal ion in the plating bath. It is not easy to obtain the desired plating film.
ここで，それぞれの金属の塩酸塩（金属塩化物）が本
発明のめっき液を使用することが的している理由として
は， １）各種金属の塩化物が，比較的無水塩を得やすいこ
と。Here, the reason why each metal hydrochloride (metal chloride) uses the plating solution of the present invention is as follows. 1) The chloride of various metals is relatively easy to obtain an anhydrous salt. .
２）有機溶媒への溶解性が他の塩に比べ優れているこ
と。2) The solubility in organic solvents is superior to other salts.
があげられる。Is raised.
これらの亜鉛金属塩，鉄族金属塩を溶解する有機溶媒
としては，誘電率が10以上の値を有することが好まし
い。有機溶媒の誘電率が10以上の値が適している理由と
しては，各種金属塩の溶解性が高いからである。The organic solvent that dissolves these zinc metal salts and iron group metal salts preferably has a dielectric constant of 10 or more. The reason why the value of the dielectric constant of the organic solvent is 10 or more is appropriate because the solubility of various metal salts is high.
また，従来法の水溶液を溶媒とした水溶液電解法によ
る亜鉛−鉄族金属合金のめっき方法の欠点であった電気
化学的に卑な金属が優先析出し，めっき浴中の金属イオ
ン組成に対する析出合金組成が異なるという異常型析出
現象は，本発明の有機溶媒を溶媒とした有機電解法によ
る亜鉛−鉄族金属合金のめっき方法を使用することによ
り改善でき，正常型析出を示す。In addition, the electrochemically noble metal, which was a disadvantage of the conventional method of plating a zinc-iron group metal alloy by an aqueous solution electrolysis method using an aqueous solution as a solvent, preferentially precipitates, and the deposited alloy has a different composition with respect to the metal ion composition in the plating bath. The abnormal precipitation phenomenon of different compositions can be improved by using the method of plating a zinc-iron group metal alloy by the organic electrolysis method using the organic solvent of the present invention as a solvent, and shows normal precipitation.
これら，本発明の有機溶媒を溶媒とした有機電解法に
よる亜鉛−鉄族金属合金のめっき方法が正常型析出を示
し，めっき浴中の金属イオン組成に対し，析出合金組成
がほぼ一致する理由としては，水溶液中での異常型析出
現象は，多量の水素イオンの放電による陰極近傍のpHが
上昇し，陰極上に亜鉛(OH)2皮膜が生成し,Niイオンの放
電が抑制されたためであると考えられる。The reason why the plating method of the zinc-iron group metal alloy by the organic electrolysis method using the organic solvent of the present invention as a solvent shows normal-type deposition, and the reason why the composition of the deposited alloy almost matches the metal ion composition in the plating bath is as follows. The reason is that the abnormal precipitation phenomenon in aqueous solution is because the pH near the cathode increased due to the discharge of a large amount of hydrogen ions, the zinc (OH) 2 film was formed on the cathode, and the discharge of Ni ions was suppressed. it is conceivable that.
また，本発明において，過塩素酸塩類等の支持塩は，
めっき浴の導電性を上昇させるためにめっき液に添加さ
れる。このような本発明のめっき液を用いた方法によれ
ば，電気化学的に卑な金属の優先析出が防止でき，めっ
き浴中の金属イオン組成に対する析出合金組成がほぼ一
致する正常型析出現象を示すため，従来法に比べ，合金
の組成制御が容易で，かつ簡便なめっき浴の管理が可能
な亜鉛−鉄族金属合金のめっき方法を得ることができ
る。In the present invention, supporting salts such as perchlorates are
It is added to the plating solution to increase the conductivity of the plating bath. According to such a method using the plating solution of the present invention, preferential deposition of an electrochemically base metal can be prevented, and a normal-type precipitation phenomenon in which the composition of the deposited alloy substantially matches the metal ion composition in the plating bath. Therefore, compared with the conventional method, it is possible to obtain a zinc-iron group metal alloy plating method in which the composition of the alloy can be easily controlled and the plating bath can be easily controlled.
（実施例） 以下に，本発明の実施例について説明する。Example An example of the present invention will be described below.
亜鉛金属塩として亜鉛の塩化物ZnCl2，鉄族金属塩と
して鉄族金属の塩化物FeCl3，NiCl2のいずれも無水物を
用い，非水溶媒としてメタノール，エタノール，ホルム
アミド，ジメチルホルムアミドを窒素下減圧蒸留して精
製したものを用いた。Zinc chloride ZnCl 2 as zinc metal salt, iron group metal chloride FeCl 3 and NiCl 2 as anhydrous iron group metal salt, and anhydrous methanol, ethanol, formamide, dimethylformamide as non-aqueous solvent. Purified by distillation under reduced pressure was used.
これらの化合物を全金属イオン濃度を0.5mol/lとなる
よう第１表記載の所定量混合し，めっき浴とした。電解
容器は密閉式のものを用いた。These compounds were mixed in a predetermined amount shown in Table 1 so that the total metal ion concentration was 0.5 mol / l, and the mixture was used as a plating bath. The electrolytic vessel used was a closed type.
陽極には白金板，陰極には圧延薄銅板（たて2cm,よこ
2cm,厚さ0.1cm）を用いて，マグネチックスターラーで
攪拌しながら直流電流で浴温25〜50℃，で定電流電解し
た。A platinum plate for the anode and a rolled thin copper plate (2 cm long, horizontal) for the cathode
(2 cm, 0.1 cm thick), and a constant-current electrolysis was performed at a bath temperature of 25 to 50 ° C. with a direct current while stirring with a magnetic stirrer.
陰極上に得られためっき膜は，金属光沢のある平滑な
ものであった。The plating film obtained on the cathode was smooth with a metallic luster.
メタノール浴において，基本浴組成から浴中の全金属
イオン濃度を0.5mol/l一定としてZnとNiとの濃度比を変
化させたときの電着合金組成を第１図に示す。FIG. 1 shows the composition of the electrodeposited alloy when the concentration ratio of Zn and Ni was changed while keeping the total metal ion concentration in the bath constant at 0.5 mol / l from the basic bath composition in the methanol bath.
図中の破線は組成参照線であり，この線上では浴中の
金属イオン組成と析出合金組成が等しいことを示す。ま
た，より貴な金属の含有率がこの線の上部に位置する場
合は，正常型析出，下部に位置する場合は異常型析出が
起こっていることになる。The dashed line in the figure is a composition reference line, on which the metal ion composition in the bath and the precipitated alloy composition are equal. When the content of the noble metal is located at the top of this line, normal-type precipitation occurs, and when it is located below the line, abnormal-type precipitation occurs.
第１図から，有機溶媒浴で電析させたものが，全浴組
成範囲にわたって正常型析出を示すことが，明らかであ
る。From FIG. 1, it is clear that the electrodeposited solution in the organic solvent bath shows normal type deposition over the entire bath composition range.
（発明の効果） 以上説明したように，本発明の亜鉛金属塩と鉄族金属
塩とを可溶化する有機溶媒の１種，または２種以上の混
合溶媒からなるめっき液を用いた有機電解めっき法によ
る亜鉛−鉄族金属合金めっき方法により，水溶液を溶媒
とした水溶液電解による亜鉛−鉄族金属合金のめっきに
おける電気化学的に卑な金属が優先析出するという異常
型析出現象が防止でき，正常型析出を示し，めっき浴中
の金属イオン組成と析出合金組成がほぼ一致し，目的の
析出合金組成の制御が容易となり，めっき浴中の金属イ
オンの濃度管理が容易となる。 (Effect of the Invention) As described above, organic electrolytic plating using a plating solution comprising one or more mixed solvents of an organic solvent for solubilizing a zinc metal salt and an iron group metal salt of the present invention. The zinc-iron group metal alloy plating method by the method can prevent the abnormal type precipitation phenomenon in which the electrochemically noble metal is preferentially deposited in the plating of the zinc-iron group metal alloy by the electrolysis of an aqueous solution using an aqueous solution as a solvent. This indicates that the metal ion composition in the plating bath is almost the same as the composition of the deposited alloy, which makes it easy to control the desired composition of the deposited alloy and to easily control the concentration of metal ions in the plating bath.
また，本発明によれば，めっき液を完全に非水系とす
ることができるので，高品質の合金膜を得ることができ
る。Further, according to the present invention, since the plating solution can be completely non-aqueous, a high quality alloy film can be obtained.
第１図は溶中の金属イオン濃度と電析合金組成との関係
を示す図である。FIG. 1 is a view showing the relationship between the concentration of metal ions during melting and the composition of an electrodeposited alloy.
Claims (5)
ためっき液において，前記溶媒は有機溶媒であることを
特徴とする亜鉛−鉄族金属合金めっき液。1. A zinc-iron group metal alloy plating solution wherein a zinc metal salt and an iron group metal salt are dissolved in a solvent, wherein the solvent is an organic solvent.
めっき液において，前記亜鉛金属塩，および前記鉄族金
属塩が共に塩化物であることを特徴とする亜鉛−鉄族金
属合金めっき液。2. A zinc-iron group metal plating solution according to claim 1, wherein said zinc metal salt and said iron group metal salt are both chlorides. Alloy plating solution.
属合金めっき液において，前記有機溶媒は誘電率が10以
上の値を有することを特徴とする亜鉛−鉄族金属合金め
っき液。3. A zinc-iron group metal alloy plating solution according to claim 1, wherein said organic solvent has a dielectric constant of 10 or more. liquid.
の亜鉛−鉄族金属合金めっき液において，前記めっき液
は支持塩として過塩素酸塩類を含むことを特徴とする亜
鉛−鉄族金属合金めっき液。4. A zinc-iron group metal alloy plating solution according to claim 1, wherein said plating solution contains perchlorates as a supporting salt. Zinc-iron group metal alloy plating solution.
族金属合金めっき液を用いて，基板上に亜鉛−鉄族合金
めっき膜を電着させる方法において，前記溶媒は有機溶
媒であることを特徴とする亜鉛−鉄族金属合金めっき方
法。5. A method for electrodepositing a zinc-iron group alloy plating film on a substrate using the zinc-iron group metal alloy plating solution according to any one of claims 1 to 4, wherein the solvent is an organic solvent. A zinc-iron group metal alloy plating method, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17542390A JP2860916B2 (en) | 1990-07-04 | 1990-07-04 | Zinc-iron group metal alloy plating solution and zinc-iron group metal alloy plating method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17542390A JP2860916B2 (en) | 1990-07-04 | 1990-07-04 | Zinc-iron group metal alloy plating solution and zinc-iron group metal alloy plating method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0466690A JPH0466690A (en) | 1992-03-03 |
| JP2860916B2 true JP2860916B2 (en) | 1999-02-24 |
Family
ID=15995840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17542390A Expired - Lifetime JP2860916B2 (en) | 1990-07-04 | 1990-07-04 | Zinc-iron group metal alloy plating solution and zinc-iron group metal alloy plating method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2860916B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300382C (en) * | 2004-04-12 | 2007-02-14 | 昆明理工大学 | Steel components and parts covered by Zn-Fe-RE cladding material, electroplating method and electrolyte |
| DE102012110972B3 (en) * | 2012-11-14 | 2014-03-06 | Muhr Und Bender Kg | A method of making a product from flexibly rolled strip material and product from flexibly rolled strip material |
-
1990
- 1990-07-04 JP JP17542390A patent/JP2860916B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0466690A (en) | 1992-03-03 |
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