JPS63241194A - Electroplating method for iron and zinc alloy - Google Patents
Electroplating method for iron and zinc alloyInfo
- Publication number
- JPS63241194A JPS63241194A JP7509587A JP7509587A JPS63241194A JP S63241194 A JPS63241194 A JP S63241194A JP 7509587 A JP7509587 A JP 7509587A JP 7509587 A JP7509587 A JP 7509587A JP S63241194 A JPS63241194 A JP S63241194A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- iron
- appearance
- zinc alloy
- bath
- 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
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 31
- 238000009713 electroplating Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 15
- 229910000640 Fe alloy Inorganic materials 0.000 title 1
- 238000007747 plating Methods 0.000 claims abstract description 63
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 10
- 239000006174 pH buffer Substances 0.000 claims abstract description 9
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 abstract description 18
- 150000002500 ions Chemical class 0.000 abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 abstract description 2
- 239000004310 lactic acid Substances 0.000 abstract description 2
- 235000014655 lactic acid Nutrition 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 150000002334 glycols Chemical class 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229940001447 lactate Drugs 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OYKBQNOPCSXWBL-SNAWJCMRSA-N n-hydroxy-3-[(e)-3-(hydroxyamino)-3-oxoprop-1-enyl]benzamide Chemical compound ONC(=O)\C=C\C1=CC=CC(C(=O)NO)=C1 OYKBQNOPCSXWBL-SNAWJCMRSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は、鋼ストリップ等に対しても外観ムラの無い
均一付着量・均一組成のめっき皮膜を安定して形成させ
ることが可能な“鉄−亜鉛合金電気めっき方法”に関す
るものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to the production of "iron" which can stably form a plating film with a uniform coating amount and a uniform composition without any uneven appearance even on steel strips, etc. - Zinc alloy electroplating method”.
〈背景技術〉
近年、例えば自動車用等として使用される防錆鋼板の主
流は、塗装性や耐食性に優れているとの理由から鉄−亜
鉛合金めっき鋼板やニッケルー亜鉛合金めっき鋼板に移
りつつあり、中でも塗膜の耐剥離性や化成処理性等の観
点から鉄−亜鉛合金めっき鋼板が多用されるようになっ
てきた。<Background technology> In recent years, the mainstream of rust-proof steel sheets used, for example, in automobiles, has been shifting to iron-zinc alloy coated steel sheets and nickel-zinc alloy coated steel sheets, due to their superior paintability and corrosion resistance. Among these, iron-zinc alloy plated steel sheets have come to be frequently used from the viewpoint of the peeling resistance of the coating film and the chemical conversion treatment properties.
しかし、鉄−亜鉛合金めっきには主として硫酸塩系電気
めっき浴が用いられるが、連続ストリップの電気めっき
を行う場合にはストリップの流れ方向に“流れ模様状の
外観ムラ（以下、単に゛外観ムラ°と称する）”が発生
すると言う不都合があり、これが鉄−亜鉛合金めっき鋼
板を工業生産する上で大きな障害となっていた。However, sulfate-based electroplating baths are mainly used for iron-zinc alloy plating, but when electroplating continuous strips, "flow pattern-like appearance unevenness" (hereinafter simply referred to as "appearance unevenness") occurs in the flow direction of the strip. This has been a major hindrance in the industrial production of iron-zinc alloy coated steel sheets.
この鉄−亜鉛合金めっき固有の外観ムラは、その発生メ
カニズムについては不明であるが、水の電気分解によっ
てめっき界面で生じるＨ、ガスが影響するとも云われて
いる。Although the mechanism by which this appearance unevenness inherent to iron-zinc alloy plating occurs is unknown, it is said that H and gas generated at the plating interface due to water electrolysis have an effect.
勿論、これまでにも鉄−亜鉛合金電気めっきの外観向上
策が様々な観点から検討されてきており、例えばめっき
浴にデキストリンやゼラチン等の添加剤や界面活性剤（
ＣｂＨａ（Ｃ０２）ＣａＨ３ＳＯａＮａやＣ＋ｔＨｚｓ
ＯＳＯＪａの陰イオン界面活性剤等）を添加する方法、
或いはめっき浴のｐ Ｈを低下する方法等が試みられた
が、陰イオン界面活性剤の添加により光沢性はかなり良
くなるとの報告は見られるものの、外観ムラを解消する
には至らなかった。Of course, measures to improve the appearance of iron-zinc alloy electroplating have been studied from various perspectives. For example, additives such as dextrin and gelatin, and surfactants (
CbHa(C02)CaH3SOaNa and C+tHzs
OSOJa anionic surfactant, etc.)
Alternatively, attempts have been made to lower the pH of the plating bath, but although there have been reports that the addition of anionic surfactants considerably improves gloss, the unevenness in appearance has not been resolved.
また、これとは別に、鉄−亜鉛めっき浴に対して水酸Ｍ
（−０Ｈ）を１個以上有し、しかも実質的にスルホン酸
基（−Ｓ Ｏ、）を有しない環式化合物の０．０ＯＯ０
５〜０．１ ｍｏ ｌ ／ ｉ！を添加することで、鉄
−亜鉛めっき浴中のＦｅ”がｐ ｅ ２ ＊に酸化され
るのを防止すると共に高電流密度化を可能とし、これに
よってめっきの外観を向上させようとの提案がなされて
いる（特開昭６０−１６９５８７号）。Separately, hydroxyl M
0.0OO0 of a cyclic compound having one or more (-0H) and substantially no sulfonic acid group (-SO,)
5-0.1 mol/i! It has been proposed that the addition of ``Fe'' in the iron-zinc plating bath can be prevented from being oxidized to p e 2 *, and that high current density can be achieved, thereby improving the appearance of the plating. (Japanese Unexamined Patent Publication No. 169587/1987).
更に、鉄−亜鉛めっき浴中にポリオキシエチレン誘導体
化合物及びポリオキシプロピレン誘導体化合物の１種又
は２種以上を合計量で０．０１〜１０ｇｅｌ添加し、め
っき表面光沢の向上のみならず、Ｆｅ３＋イオンの還元
溶解反応の選択性改善、並びにＦｅ”イオンの空気酸化
及び陽極酸化の防止を図る方法に関する提案も見られる
（特開昭６０−１５５６９７号）。Furthermore, a total amount of 0.01 to 10 gel of one or more polyoxyethylene derivative compounds and polyoxypropylene derivative compounds is added to the iron-zinc plating bath, which not only improves the plating surface gloss but also improves Fe3+ ions. There has also been a proposal for a method for improving the selectivity of the reduction and dissolution reaction of Fe'' ions and for preventing air oxidation and anodic oxidation of Fe'' ions (Japanese Patent Laid-Open No. 155697/1983).
或いは更に、鉄−亜鉛合金めっき硫酸塩浴中にポリビニ
ルアルコール及びポリビニルアルコール誘導体の１種又
は２種以上を添加することによって鉄−亜鉛合金めっき
特有の異常電析特性を正常電析特性に変え、これにより
めっき浴中のＦｅ”イオンを抑制することによってめっ
き皮膜組成のバラキラを軽減し、外観均一性が良好な光
沢のあるめっき皮膜を得ると共に、イオン補給時の金属
ＦｅやＺｎのＦｅ３＋還元反応選択性を向上させること
も提案されている（特開昭６１−２５０１９０号）。Alternatively, by adding one or more of polyvinyl alcohol and polyvinyl alcohol derivatives to the iron-zinc alloy plating sulfate bath, abnormal electrodeposition characteristics peculiar to iron-zinc alloy plating are changed to normal electrodeposition characteristics, This suppresses Fe'' ions in the plating bath, reduces variations in the plating film composition, provides a glossy plating film with good appearance uniformity, and reduces the Fe3+ reduction reaction of metal Fe and Zn during ion replenishment. It has also been proposed to improve selectivity (Japanese Patent Application Laid-open No. 250190/1983).
しかしながら、これらの方法は何れも“硫酸浴系鉄−亜
鉛合金電気めっき”におけるＦｅ３＋対策としての還元
効率の上昇や、単なるめっき外観の均一性、或いは光沢
性の向上を目指したものに過ぎず、−見、同一線上に位
置するかの如く認識されがちな前記「外観ムラ」まで十
分に改善されるものではなかった。However, all of these methods merely aim to increase the reduction efficiency as a countermeasure for Fe3+ in "sulfuric acid bath-based iron-zinc alloy electroplating", or simply to improve the uniformity of the plating appearance or gloss. - The above-mentioned "unevenness in appearance", which tends to be perceived as if they are located on the same line, was not sufficiently improved.
〈問題点を解決する手段〉
そこで、本発明者等はまず前記「外観ムラ」そのものの
解明を目指し、Ｓ Ｔ Ｍ Ｓ （Ｓｅｃｏｎｄａｒｙ
ＩｏｎＭａｓｓ ５ｐｅｃｔｒｏｓｃｏｐｙ）やＥ
Ｐ Ｍ Ａ （Ｈｌｅｃｔｏｒｏｎ Ｐｒ−ｏｂｅ Ｘ
−ｒａｙ Ｍｉｃｒｏ Ａｎａｌｙｓｅｒ）等の物理分
析手段を用いて調査したところ、「前記ムラ部はめっき
の付＠量が少なく、かつ亜鉛濃度も高くなっている」と
の事実を確認したのである。そして、この事実から、「
先に述べた各めっき外観改善策で外観ムラが完全に解消
されなかったのは、製品特性の点から“めっき外観の均
一性”や“光沢性の向上１以上に重要であるところの“
めっきの均一付着性”や”めっき皮膜の均一組成”面で
の改善が十分になされていないからである」との結論に
到達した。<Means for solving the problem> Therefore, the present inventors first aimed to clarify the above-mentioned "appearance unevenness" itself, and
IonMass 5pectroscopy) and E
PMA (Hlectoron Pr-obe X
As a result of investigation using physical analysis means such as a ray micro analyzer, it was confirmed that ``the uneven area has a small amount of plating and also has a high zinc concentration.'' And from this fact,
The reason why the appearance unevenness was not completely eliminated by each of the plating appearance improvement measures mentioned above is that "uniformity of plating appearance" and "improvement of gloss," which are more important than "uniformity of plating appearance" from the point of view of product characteristics.
They concluded that this is because sufficient improvements have not been made in terms of ``uniform adhesion of plating'' and ``uniform composition of plating film.''
また、特に鉄−亜鉛合金めっきの目付量が低い（１〜１
０ｇ／ｍ）場合には、このムラ部が耐食性能や塗装性能
に影響を及ぼすことも判明した。In addition, the basis weight of iron-zinc alloy plating is particularly low (1 to 1
It was also found that in the case of 0 g/m), this uneven portion affects corrosion resistance performance and coating performance.
このようなことから、本発明者等は、鉄−亜鉛合金めっ
きの際に見られる“めっき付着量やめっき皮膜組成の不
均一゛を改善して前記外観ムラを抑える手段を見出すべ
く更なる研究を行ったところ、鉄−亜鉛合金めっき固有
の外観ムラ（即ち膜厚の不均一）は下記のメカニズムで
発生することが明らかとなったのである。For these reasons, the present inventors conducted further research in order to find a means to suppress the unevenness in appearance by improving the "non-uniformity of the coating amount and coating film composition" observed during iron-zinc alloy plating. As a result, it became clear that the appearance unevenness (ie, non-uniformity in film thickness) inherent to iron-zinc alloy plating occurs through the following mechanism.
即ち、鉄−亜鉛合金めっき浴中のＦｅ”″−イオンは、
空気酸化もしくは陽極酸化によりＦｅ”イオンに変化す
るため、鉄−亜鉛合金めっき浴のＦｅ”ｆＱ度が上昇す
る。また、一般に亜鉛系合金めっきでは電流効率が８０
％以下と良好でなく、電析のため以外にＨ２Ｏを電気分
解してＨ２とＯＨ−を生成するのに電気量が消費される
ため、めっき雪折界面はバルクのｐＨに比較して異常に
高いｐ Ｈとなる。That is, Fe""- ions in the iron-zinc alloy plating bath are
Since it changes into Fe'' ions by air oxidation or anodic oxidation, the Fe''fQ degree of the iron-zinc alloy plating bath increases. Additionally, in general, zinc-based alloy plating has a current efficiency of 80
% or less, which is not good, and the amount of electricity is consumed not only for electrodeposition but also for electrolyzing H2O to generate H2 and OH-, so the pH of the plating interface is abnormal compared to the bulk pH. High pH results.
従って、めっき浴中ではＦｅ”ｆ７４度が高くなるのに
伴い雪折界面で生じたＯＨ−と前記Ｆｅ３＋が反応して
雪折界面にてＦｅ（ＯＨ）３を生成することとなり、こ
れに起因してめっきの通電ムラが生じ、“めっき付着量
の不均一”や“めっき皮膜組成の不均一”を招く。Therefore, in the plating bath, as the Fe'f74 degree increases, the OH- generated at the snow-fold interface reacts with the Fe3+ to generate Fe(OH)3 at the snow-fold interface. This causes uneven electrical conduction of the plating, leading to "uneven plating amount" and "uneven plating film composition."
このため、めっきの不均一付着対策として「めっき浴中
のバルクのｐＨを低下させることによりめっき雪折界面
でのｐＨ上昇を抑制することが有効である」と考えられ
がちであるが、本発明者等の更なる検討結果は、「この
ようなめっき浴ｐｔ−ｒの低下は、逆にめっきの電流効
率を低下させることとなって界面のＯＨ−生成量を増大
させ才しまう上、製造面から見ると電力コストの上昇を
招くものであり、しかも、一定膜厚の鉄−亜鉛合金めっ
き皮膜を得るためには電流効率が低下した分を電気量で
補う必要があり、それ故に陽極酸化量も増大してＦｅ’
＋の増加につながって好ましくない」との事実を明らか
にすることとなった。For this reason, it is often thought that ``suppressing the increase in pH at the plating interface by lowering the bulk pH in the plating bath is effective as a countermeasure against uneven adhesion of plating,'' but the present invention The results of further study by these authors indicate that ``Such a decrease in plating bath pt-r will conversely reduce the current efficiency of plating, increase the amount of OH- produced at the interface, and also cause problems in terms of manufacturing. This results in an increase in electricity costs.Moreover, in order to obtain an iron-zinc alloy plating film with a constant thickness, it is necessary to compensate for the decrease in current efficiency with electricity, and therefore the amount of anodic oxidation increases. also increases and Fe'
``This is undesirable as it leads to an increase in ``+''.
従って、本発明者等は、均一なめっき付着量及び皮膜組
成を有した“外観ムラの無い鉄−亜鉛合金めっき”を安
定して実施するためには、めっき浴ｐＨの低下を図る以
外の手段を導入する必要があるとの観点に立って一層の
研究を重ねた結果、「鉄−亜鉛合金めっき作業に際し、
めっき浴中に特定量のｐＨ緩衝剤と非イオン系界面活性
剤とを同時に添加してめっきを行うと、先にに述べたよ
うな不都合は一掃され、付着量及び組成が均一で外観ム
ラが無く、しかも光沢の良好なめっき皮膜を安定して形
成させることができる」との知見を得るに至ったのであ
る。Therefore, the present inventors believe that in order to stably perform "iron-zinc alloy plating with uniform appearance and uniform coating weight and film composition," there is no need to reduce the pH of the plating bath. As a result of further research from the perspective of the need to introduce
If plating is performed by adding a specific amount of pH buffer and nonionic surfactant to the plating bath at the same time, the above-mentioned disadvantages will be eliminated, and the coating amount and composition will be uniform and the appearance will not be uneven. They have come to the conclusion that it is possible to stably form a plating film with good gloss without the need for oxidation.
この発明は、上記知見に基づいてなされたものであり、
硫酸浴系鉄−亜鉛合金めっき浴中に、ｐＨ緩衝剤の１種
又は２種以上を１０〜５００ｇ／Ｊ添加すると共に、非
イオン系の界面活性剤の１種又は２種以上をも０．１〜
１Ｏｐｐ＊の割合で添加して電気めっきすることにより
、均−付着性及び均一組成を有し、かつ光沢外観を呈す
ると共に、外観ムラの無い外観均一性を有する鉄−亜鉛
合金めっきを安定して形成し得るようにした点、
に特徴を有するものである。This invention was made based on the above findings, and includes adding 10 to 500 g/J of one or more pH buffers to a sulfuric acid bath-based iron-zinc alloy plating bath, and One or more surfactants of 0.1~
By electroplating with addition at a ratio of 1 Opp*, it is possible to stably produce an iron-zinc alloy plating that has uniform adhesion, a uniform composition, a glossy appearance, and a uniform appearance with no unevenness. It is characterized by the fact that it can be formed.
なお、ｐＨ緩衝剤としてはクエン酸又はクエン酸塩、酢
酸又は酢酸塩、乳酸又は乳酸塩、硫酸アルミニウム並び
にＥＤＴＡ （エチレン・ジアミン・テトラ・アセテー
ト）のうちの１種又は２種以上を添加するのが好ましく
、また前記クエン酸塩。In addition, as a pH buffer agent, one or more of citric acid or citrate, acetic acid or acetate, lactic acid or lactate, aluminum sulfate, and EDTA (ethylene diamine tetra acetate) may be added. is preferred, and also the citrate salt.
酢酸塩或いは乳酸塩の種類は格別に制限されるものでは
ないが、クエン酸塩としてはクエン酸ナトリウムが、酢
酸塩としては酢酸ナトリウムが、そして乳酸塩としては
乳酸ナトリウムが好適である。Although the type of acetate or lactate is not particularly limited, sodium citrate is preferred as the citrate, sodium acetate is preferred as the acetate, and sodium lactate is preferred as the lactate.
一方、非イオン系の界面活性剤としてはポリエチレング
リコール、ポリエチレングリコール誘導体、ポリプロピ
レングリコール並びにポリプロピレングリコール誘導体
のうちの１種又は２種以上を添加するのが好ましい。On the other hand, as the nonionic surfactant, it is preferable to add one or more of polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, and polypropylene glycol derivatives.
ここで、ポリエチレングリコール誘導体とは式％式％）
で表わされるものであり、ポリプロピレングリコール誘
導体とは式
％式％
そして、この発明の方法においてｐＨ緩衝剤の添加量及
び非イオン系の界面活性剤の添加割合を前記の如くに限
定した理由は次の通りである。Here, the polyethylene glycol derivative is represented by the formula (% formula %), and the polypropylene glycol derivative is represented by the formula (% formula %). The reason for limiting the addition ratio as described above is as follows.
１）ｐＨ緩衝剤
ｐＨ緩衝剤の添加割合が１０ｇ＃！未満ではその効果を
示さず、一方、５００ｇ＃’を超えて添加してもその効
果が添加量に見合う程には向上しないことから、ｐＨ緩
衝剤の添加割合は１０〜５００ｇｅｌと限定した。1) pH buffer The addition ratio of pH buffer is 10g#! The addition ratio of the pH buffer was limited to 10 to 500 gel because the effect is not shown if it is less than 500 g#', and the effect does not improve to an extent commensurate with the amount added if it is added in excess of 500 g#'.
ｉｉ ）非イオン系の界面活性剤
非イオン系の界面活性剤の添加割合が０、ｌｐｐｍ未満
ではその添加効果が表われず、一方、１０ｐｐｍを超え
て添加するとめっき皮膜のパウダリング現象が起きる等
、加工時の問題が生じることから、非イオン系の界面活
性剤の添加割合は０．１〜１０ｐｐｍと限定した。ii) Non-ionic surfactant If the addition ratio of non-ionic surfactant is less than 0.1 ppm, the effect of the addition will not appear, while if it is added in excess of 10 ppm, powdering of the plating film will occur, etc. Since problems may occur during processing, the proportion of nonionic surfactant added was limited to 0.1 to 10 ppm.
ところで、前記ｐＨＷｋ衝剤及び非イオン系の界面活性
剤を添加する硫酸浴系鉄−亜鉛合金めっき浴の基本組成
や、その他のめっき条件としては、これまで知られてい
るものの何れを採用しても良いことは言うまでもない。By the way, as for the basic composition of the sulfuric acid bath-based iron-zinc alloy plating bath to which the pHWk buffer agent and nonionic surfactant are added, and other plating conditions, any of those known so far have been adopted. Needless to say, it's a good thing.
次いで、この発明を実施例によって具体的に説明する。Next, the present invention will be specifically explained with reference to Examples.
〈実施例〉
板厚０．８ｍｎの冷延鋼板を用意し、第１表に示す電気
めっき条件で鉄−亜鉛合金めっきを行った。<Example> A cold-rolled steel sheet with a thickness of 0.8 mm was prepared, and iron-zinc alloy plating was performed under the electroplating conditions shown in Table 1.
なお、この時のめっき浴温度は５０℃に保持され、液流
速は１ ｍ／ｓｅｃに調整された。Note that the plating bath temperature at this time was maintained at 50° C., and the liquid flow rate was adjusted to 1 m/sec.
このような鉄−亜鉛合金電気めっき処理により得られた
めっき皮Ｈ５！のＦｅ含含率率めっき付着量。Plated skin H5 obtained by such iron-zinc alloy electroplating treatment! Fe content and plating adhesion amount.
均一付着性・均一組成性、並びにめっき外観を第１表に
併せて示す。Uniform adhesion, uniform composition, and plating appearance are also shown in Table 1.
なお、めっき皮膜の均一付着性・均一組成性は、ＥＰＭ
ＡによってＦｅ及びＺｎ元素のマツピング解析を実施し
評価した（ＥＰＭＡ条件：電圧１５ｋ Ｖ 。In addition, the uniform adhesion and uniform composition of the plating film are determined by EPM.
Mapping analysis of Fe and Zn elements was performed and evaluated using A (EPMA conditions: voltage 15 kV.
電流０．０１μＡ、測定ステップ２０ ｐ ｍ ・２５
６ Ｘ ２５６゜測定面積５１ｍＸ５ｍｍ）、そして、
評価結果は○：均−付着性・均一組成性が良好。Current 0.01 μA, measurement step 20 p m ・25
6 x 256° measurement area 51m x 5mm), and
The evaluation results are ○: Good uniform adhesion and uniform composition.
Δ：均−付着性・均一組成性が普通。Δ: Normal adhesion and uniform composition.
×：均一付着性・均一組成性が劣る。×: Poor uniform adhesion and uniform composition.
の３段階で表示した。It was displayed in three stages.
また、めっきの外観は目視により評価し、○：外観の均
一性が良好で光沢有り。In addition, the appearance of the plating was visually evaluated. ○: Appearance had good uniformity and was glossy.
△：外観の均一性が良好で光沢なし。△: Good uniformity of appearance and no gloss.
×：外観の均一性が不良（カスリ模様有り）。×: Poor uniformity of appearance (scratching pattern present).
の３段階で表示した。It was displayed in three stages.
第１表に示される結果からも明らかなように、本発明の
条件通りのめっき処理を行った場合にはめっき皮膜の均
一付着性・均−組成性及びめっき外観とも非常に良好な
鉄−亜鉛合金めっき製品か得られるのに対して、めっき
浴中にｐＨｆＪｔ衝剤及び非イオン系の界面活性剤の複
合添加がなされなかった場合にはめっき皮膜の均一付着
性・均一組成性に劣ることとなり、まためっき外観も劣
る恐れのあることが分かる。As is clear from the results shown in Table 1, when the plating treatment is carried out according to the conditions of the present invention, the iron-zinc coating has very good uniform adhesion, homogeneous composition, and appearance of the plating film. While an alloy plated product can be obtained, if a combination of pHfJt buffer and nonionic surfactant is not added to the plating bath, the uniform adhesion and composition of the plating film will be poor. , it can be seen that the appearance of the plating may also be inferior.
く効果の総括〉
以上に説明した如く、この発明によれば、これまで困難
であった鉄−亜鉛合金めっきの均−付着性及び均一組成
性が十分に達成されると共に、優れた光沢外観も確保さ
れ、外観並びに耐食性や密着性等の面で一段と性能が向
上した鉄−亜鉛合金めっき製品を安定して量産すること
が可能となるなど、産業上極めて有用な効果がもたらさ
れるのである。Summary of Effects> As explained above, according to the present invention, it is possible to sufficiently achieve uniform adhesion and uniform composition of iron-zinc alloy plating, which had been difficult until now, and also to achieve an excellent glossy appearance. This brings about extremely useful effects industrially, such as making it possible to stably mass-produce iron-zinc alloy plated products with improved performance in terms of appearance, corrosion resistance, adhesion, etc.
Claims (1)
又は２種以上を１０〜５００ｇ／ｌ添加すると共に、非
イオン系の界面活性剤の１種又は２種以上をも０．１〜
１０ｐｐｍの割合で添加して電気めっきすることを特徴
とする、鉄−亜鉛合金電気めっき方法。In addition to adding 10 to 500 g/l of one or more pH buffers to the sulfuric acid bath-based iron-zinc alloy plating bath, one or more nonionic surfactants are also added at 0.0 g/l. 1~
A method for electroplating an iron-zinc alloy, characterized in that electroplating is carried out with addition at a rate of 10 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7509587A JPS63241194A (en) | 1987-03-28 | 1987-03-28 | Electroplating method for iron and zinc alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7509587A JPS63241194A (en) | 1987-03-28 | 1987-03-28 | Electroplating method for iron and zinc alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63241194A true JPS63241194A (en) | 1988-10-06 |
Family
ID=13566265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7509587A Pending JPS63241194A (en) | 1987-03-28 | 1987-03-28 | Electroplating method for iron and zinc alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63241194A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100417615B1 (en) * | 1999-08-14 | 2004-02-05 | 주식회사 포스코 | Method for making Zn electrodeposit additive |
| CN104726924A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten multi-walled carbon nanotube (MWCNT) composite plating solution, plated film and preparation method thereof |
| CN104726925A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Method for preparing HNTs/Ni-W coating film |
| CN104726907A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten graphene oxide (GO) composite plating solution, plated film and preparation method thereof |
| CN104726908A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten-mica composite plating solution, plating film and preparation method thereof |
| CN104911652A (en) * | 2015-04-16 | 2015-09-16 | 西南石油大学 | Nickel, tungsten and graphene composite plating solution, plated film and making method of plated film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5751283A (en) * | 1980-09-12 | 1982-03-26 | Nippon Steel Corp | Electroplating method for zinc-iron alloy |
| JPS60155697A (en) * | 1984-01-23 | 1985-08-15 | Nippon Steel Corp | Method for electroplating iron-zinc alloy |
| JPS6130695A (en) * | 1984-07-20 | 1986-02-12 | Kawasaki Steel Corp | Manufacture of zn-fe alloy electroplated steel sheet having fine appearance and color tone |
-
1987
- 1987-03-28 JP JP7509587A patent/JPS63241194A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5751283A (en) * | 1980-09-12 | 1982-03-26 | Nippon Steel Corp | Electroplating method for zinc-iron alloy |
| JPS60155697A (en) * | 1984-01-23 | 1985-08-15 | Nippon Steel Corp | Method for electroplating iron-zinc alloy |
| JPS6130695A (en) * | 1984-07-20 | 1986-02-12 | Kawasaki Steel Corp | Manufacture of zn-fe alloy electroplated steel sheet having fine appearance and color tone |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100417615B1 (en) * | 1999-08-14 | 2004-02-05 | 주식회사 포스코 | Method for making Zn electrodeposit additive |
| CN104726924A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten multi-walled carbon nanotube (MWCNT) composite plating solution, plated film and preparation method thereof |
| CN104726925A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Method for preparing HNTs/Ni-W coating film |
| CN104726907A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten graphene oxide (GO) composite plating solution, plated film and preparation method thereof |
| CN104726908A (en) * | 2015-03-25 | 2015-06-24 | 西南石油大学 | Nickel-tungsten-mica composite plating solution, plating film and preparation method thereof |
| CN104911652A (en) * | 2015-04-16 | 2015-09-16 | 西南石油大学 | Nickel, tungsten and graphene composite plating solution, plated film and making method of plated film |
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