JPH0768633B2 - Method for producing iron-zinc alloy electroplated steel - Google Patents
Method for producing iron-zinc alloy electroplated steelInfo
- Publication number
- JPH0768633B2 JPH0768633B2 JP63062923A JP6292388A JPH0768633B2 JP H0768633 B2 JPH0768633 B2 JP H0768633B2 JP 63062923 A JP63062923 A JP 63062923A JP 6292388 A JP6292388 A JP 6292388A JP H0768633 B2 JPH0768633 B2 JP H0768633B2
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- alloy
- zinc alloy
- ions
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Description
【発明の詳細な説明】 ＜産業上の利用分野＞ この発明は、塗装仕上がり性（鮮映性）及びめっき皮膜
均質性等、外観性能に優れた鉄−亜鉛合金（Fe−Zn合
金）電気めっき鋼材の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention is an electroplating of iron-zinc alloy (Fe-Zn alloy) which is excellent in appearance performance such as coating finish (visibility) and plating film homogeneity. The present invention relates to a steel material manufacturing method.
＜従来技術とその課題＞ Fe−Zn合金めっき鋼材は、その優れた塗装性や耐食性の
故に、近年では自動車用防錆鋼板の主流を占めるように
なってきた。<Prior Art and Its Problems> Fe-Zn alloy plated steel has become the mainstream of rustproof steel sheets for automobiles in recent years because of its excellent paintability and corrosion resistance.
しかし、最近、これら防錆鋼板に対し、単に塗装性や耐
食性のみか表面外観やめっき皮膜の高い均質性、特に自
動車の車体外板用としては“塗装後外観性能”に優れる
ことが極めて重要な要素として要求されるようになって
きた。However, recently, it is extremely important for these rust-proof steel sheets to have not only excellent paintability and corrosion resistance, but also high surface appearance and high homogeneity of the plating film, especially in "post-painting appearance performance" for car body outer panels. It has come to be required as an element.
これに対して、前記Fe−Zn合金めっきでは電析結晶が粗
大化し易くて（結晶粒径が0.5〜1.0μｍφ程度）光沢感
に劣るばかりでなく、操業条件の変動により該結晶粒径
やめっきの付き回り性が変わり易い等、表面均一性に十
分満足できるものではなかった。On the other hand, in the Fe-Zn alloy plating, not only the electrodeposited crystals are easily coarsened (the crystal grain size is about 0.5 to 1.0 μmφ) but the gloss feeling is not good, but the crystal grain size and the plating are changed due to the fluctuation of operating conditions. The surface throwing power was not easy to change and the surface uniformity was not satisfactory.
ところで、Fe−Zn合金めっきにおいては、めっき浴中の
鉄イオン挙動がその表面外観やめっき均一性に大きな影
響を及ぼすことが知られている。By the way, in Fe-Zn alloy plating, it is known that the behavior of iron ions in the plating bath has a great influence on the surface appearance and plating uniformity.
即ち、Fe−Zn合金めっき作業の際、めっき浴中のFe2+イ
オンは液循環時の空気巻き込みのために酸化される（Fe
2+＋1/2H2O＋1/4O2→Fe3+＋OH）ほか、不溶性陽極使用
時には陽極より発生する酸素によってもFe3+イオンに酸
化される。また、陽極における直接的な電極反応によっ
ても酸化されるので、浴中Fe3+イオン量は次第に増大す
ることとなる。そして、このFe3+イオンはめっき電流効
率を低下させるほか、めっき表面外観やめっき均一性等
の品質にも悪影響を及ぼす因子であり、塗装後外観を改
善するために上記Fe2+イオンの陽極酸化を抑制するよう
なめっき浴が望まれてきたが、未だ満足できる成果を挙
げ得なかったのである。That is, during Fe-Zn alloy plating work, Fe 2+ ions in the plating bath are oxidized due to air entrainment during liquid circulation (Fe
2+ + 1 / 2H 2 O + 1 / 4O 2 → Fe 3+ + OH) In addition, when an insoluble anode is used, it is also oxidized to Fe 3+ ions by oxygen generated from the anode. Further, since it is also oxidized by a direct electrode reaction at the anode, the amount of Fe 3+ ions in the bath will gradually increase. Then, the Fe 3+ other ions to reduce the plating current efficiency, and adversely affect factor in quality such as plated surface appearance and plating uniformity, the Fe 2+ ions of the anode to improve the post-painting appearance Although a plating bath that suppresses oxidation has been desired, it has not yet been able to achieve satisfactory results.
もっとも、めっき浴中に生成したFe3+イオンを還元する
ため、イオンの補給を兼ねて金属Feや金属Znを投入する
ことも行われてはいるが、この場合には品質的・経済的
にFe3+イオンの還元効率が高いことが望まれるにも係わ
らず、十分な還元条件のめっき浴が見出されていない現
状にあった。However, in order to reduce the Fe 3+ ions generated in the plating bath, metal Fe or metal Zn is also added to serve as ion replenishment, but in this case, it is economical and economical. Despite the desire for high reduction efficiency of Fe 3+ ions, a plating bath under sufficient reducing conditions has not yet been found.
一方、Fe−Zn合金めっきの上記状況を踏まえ、その仕上
がり性や鮮映性等の塗装外観を改善すべく塗料面での改
善策も種々検討されてきたが、これも現状では十分なも
のと言えなかった。On the other hand, based on the above situation of Fe-Zn alloy plating, various improvement measures on the paint side have been studied to improve the coating appearance such as finish and image clarity, but this is also sufficient at present. I could not say.
このようなことから、Fe−Zn合金めっきそのものの表面
外観や均質性を向上させるべく、 ｉ）めっきに際してラインスピードを増加し、これによ
って相対的なめっき液流速を上昇させると言う所謂“高
速高電流密度操業”を実施する〔「鉄と鋼」、vol.71
（1985年）のＳ−446頁，及びvol.72（1986年）のＳ−1
324頁〕， ii）めっき浴に対し、水酸基（−OH）を１個以上有し、
しかも実質的にスルホン酸基（−SO3）を有しない環式
化合物の0.00005〜0.1mol/を添加する〔特開昭60−16
9587号〕， iii）めっき浴中に対し、合計量で0.01〜10g/のポリ
オキシエチレン誘導体化合物の１種又は２種以上を添加
する〔特開昭60−155697〕， 等の手段も提案されたが、前記ｉ）の方法では塗装仕上
がり性及びめっき均質性が共に現在の要望に十分満足で
きるものとはならず、一方、前記ii）及びiii）の方法
については、表面外観の向上や浴中鉄イオンの酸化抑制
効果は認められるものの、塗装仕上がり性（鮮映性）に
ついては十分な改善効果を得られないものであった。Therefore, in order to improve the surface appearance and homogeneity of the Fe-Zn alloy plating itself, i) so-called "high speed high speed" which increases the line speed during plating and thereby increases the relative plating solution flow rate. Current density operation "[" Iron and Steel ", vol.71
(1985) page S-446 and vol.72 (1986) S-1.
324], ii) Having one or more hydroxyl groups (-OH) in the plating bath,
Moreover substantially adding 0.00005～0.1Mol / not having cyclic compounds sulfonic acid group (-SO 3) [JP 60-16
9587], iii) A total amount of 0.01 to 10 g / one or more polyoxyethylene derivative compounds is added to the plating bath [JP-A-60-155697], and other means. However, in the method i), neither the coating finish nor the plating homogeneity can sufficiently satisfy the present demands, while the methods ii) and iii) improve the surface appearance and bath. Although the effect of suppressing the oxidation of middle iron ions was recognized, it was not possible to obtain a sufficient effect of improving the paint finish (visibility).
＜課題を解決するための手段＞ 本発明者は、上述のような観点から、めっき皮膜の均一
性に優れていて良好な外観を呈し、塗装後の仕上がり
性、特に“鮮映性”が一段と優れたFe−Zn合金電気めっ
き材を安定して製造し得る方法を見出すべく、鋭意研究
を行った結果、「通常の硫酸塩系Fe−Zn合金めっき浴に
て鋼材上に直接電気めっきを行うに際して、該めっき浴
に特定量のpH緩衝剤との併用で非イオン系界面活性剤を
微量添加すると共に、特定値以上の“めっき液の被めっ
き材との相対流速”を確保すると、めっき浴中に存在す
るFe2+イオンの通電時の陽極酸化が十分に抑制されるよ
うになる上、めっき浴中へのFe2+イオン及びZn2+イオン
の供給のために金属Feや金属Znを補給する際、浴中のFe
3+イオンの還元や金属の円滑な溶解も促進される等の作
用も加わり、電析結晶が微細化してめっきの均質性が一
段と向上し、かつ塗装仕上がり性（鮮映性）が顕著に改
善されるようになる」との知見が得られたのである。<Means for Solving the Problems> From the viewpoints described above, the present inventors have found that the plating film is excellent in uniformity and has a good appearance, and that the finish after coating, especially “sharpness” is further improved. As a result of earnest research to find a method capable of stably producing an excellent Fe-Zn alloy electroplated material, as a result, "direct electroplating on a steel material is performed in a normal sulfate Fe-Zn alloy plating bath At this time, if a small amount of a nonionic surfactant is added to the plating bath in combination with a specific amount of pH buffer and a "relative flow rate of the plating solution to the material to be plated" of a specific value or more is secured, Anodic oxidation of Fe 2+ ions present in the steel during current application is sufficiently suppressed, and metal Fe and Zn are supplied to supply Fe 2+ ions and Zn 2+ ions to the plating bath. When replenishing, Fe in the bath
In addition to the effects of promoting the reduction of 3+ ions and the smooth dissolution of metals, the deposited crystals are made finer to further improve the homogeneity of plating and the finish of the coating (vividness) is significantly improved. The knowledge has been obtained.
この発明は、上記知見に基づいてなされたものであり、 「鋼材上に鉄−亜鉛合金めっき層を直接形成させる方法
であって、硫酸塩系Fe−Zn合金めっき浴中に、pH緩衝剤
の１種又は２種以上を合計量で10〜500g/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
合計量として0.1〜10ppmの割合で添加し、めっき液相対
流速0.5m/sec以上で電気めっきすることにより、塗装仕
上がり後の鮮映性並びにめっきの微細均一性が共に優れ
た高耐食性Fe−Zn合金めっき鋼材を安定製造し得るよう
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, "a method of directly forming an iron-zinc alloy plating layer on a steel material, in a sulfate-based Fe-Zn alloy plating bath, of pH buffering agent The total amount of one or more kinds is 10 to 500 g / added, and the one or more kinds of nonionic surfactants is also added at a ratio of 0.1 to 10 ppm as a total amount, and the relative flow velocity of the plating solution. By electroplating at a rate of 0.5 m / sec or more, stable corrosion-resistant Fe-Zn alloy-plated steel material with excellent image clarity after coating and fine plating uniformity can be manufactured stably. I have.
ここで、pH緩衝剤としては、クエン酸，マロン酸，シュ
ウ酸，酢酸，酒石酸，ホウ酸或いは乳酸，及びこれらの
塩類，硫酸アルミニウム，硫酸アンモニウム，リン酸，
リン酸塩（リン酸２水素ナトリウム，リン酸２水素カリ
ウム等）並びにEDTA（エチレン・ジアミン・テトラ・ア
セテート）等のうちの１種又は２種以上を添加するのが
良い。Here, as the pH buffer, citric acid, malonic acid, oxalic acid, acetic acid, tartaric acid, boric acid or lactic acid, and salts thereof, aluminum sulfate, ammonium sulfate, phosphoric acid,
It is advisable to add one or more of phosphates (sodium dihydrogen phosphate, potassium dihydrogen phosphate, etc.) and EDTA (ethylene diamine tetra acetate), etc.
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.
なお、ポリエチレングリコール誘導体とは式 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 で表わされるものであって、分子量は添加効果からみて
100〜10000のものが好ましい（より望ましくは分子量50
0〜2000のものを適用するのが良い）。The polyethylene glycol derivative is a formula The polypropylene glycol derivative is represented by the formula And the molecular weight is
100 to 10000 is preferable (more preferably molecular weight 50
It is better to apply 0 to 2000).
そして、この発明の方法においてpH緩衝剤の添加量，非
イオン系の界面活性剤の添加割合，並びにめっき液相対
流速を前記の如くに限定した理由は次の通りである。The reason for limiting the addition amount of the pH buffer agent, the addition ratio of the nonionic surfactant, and the relative flow velocity of the plating solution in the method of the present invention is as follows.
ａ） 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10〜500g/と限定した。a) pH buffering agent If the addition rate of the pH buffering agent is less than 10 g /, the effect is not exhibited, while if it is added in excess of 500 g /, the effect is not improved enough to meet the addition amount. The addition rate of the agent was limited to 10 to 500 g /.
ｂ） 非イオン系の界面活性剤 非イオン系の界面活性剤を添加割合が0.1ppm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性が劣化する等、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。b) Nonionic surfactant If the addition ratio of the nonionic surfactant is less than 0.1 ppm, the effect will not be exhibited, while if it exceeds 10 ppm, the powdering property of the plating film will deteriorate. However, since a problem occurs during processing, the addition ratio of the nonionic surfactant is limited to 0.1 to 10 ppm.
また、この界面活性剤の分子量は、添加効果からみて10
〜10000が好ましく、更に望ましくは500〜2000のものを
使用するのが良い。Also, the molecular weight of this surfactant is 10
It is preferably -10000, more preferably 500-2000.
ｃ） めっき液の相対流速 被めっき材に対するめっき液の相対流速が0.5m/sec未満
であると、塗装後の鮮映性の向上効果が小さい上、本発
明に係るめっき浴では電解条件によりパウダリング性の
劣化やめっき焼け（黒変化）の恐れもでてくる。従っ
て、めっき液の相対流速は0.5m/sec以上と定めた。c) Relative Velocity of Plating Solution When the relative velocity of the plating solution with respect to the material to be plated is less than 0.5 m / sec, the effect of improving the clarity after coating is small, and the plating bath according to the present invention is powdered depending on the electrolytic conditions. There is also a risk of ringing deterioration and plating burns (blackening). Therefore, the relative flow velocity of the plating solution was set to 0.5 m / sec or more.
第１図は、めっき液の相対流速と塗装後の鮮映性との関
係を示すグラフであるが、この第１図からも、相対流速
が0.5m/secを下回ると鮮映性が急激に劣化することが分
かる。なお、第１図の結果は次のめっき条件を基準に得
られたものである。Fig. 1 is a graph showing the relationship between the relative flow velocity of the plating solution and the sharpness after coating. From this Fig. 1 as well, sharpness of the sharpness is shown when the relative velocity is below 0.5 m / sec. It turns out that it deteriorates. The results shown in FIG. 1 were obtained based on the following plating conditions.
めっき浴組成 Na2SO4:40g/， Fe2+:50g/， Zn2+:50g/， ポリプロピレングリコール:5ppm, クエン酸ソーダ:50g/。Plating bath composition Na 2 SO 4 : 40g /, Fe 2+ : 50g /, Zn 2+ : 50g /, polypropylene glycol: 5ppm, sodium citrate: 50g /.
めっき浴pH pH1.8。Plating bath pH pH 1.8.
電流密度 80A/dm2。Current density 80A / dm 2 .
また、第１図における「鮮映性（PGD値）」は次のよう
に測定されたものである。即ち、上記条件で得られたFe
−Zn合金めっき鋼板に、 リン酸亜鉛処理（日本パーカライジング社製のPB−3080
L 〔商品名〕使用） ↓ 電着塗装:20μｍ（日本ペイント社製のＵ−100 〔商品名〕使用） ↓ 中，上塗り:80μｍ（メラミンアルキッド系樹脂） の処理を施した後、PGD（portable glossmeter of dist
inction）計で鮮映性を測定して得た値である。Further, the "vividness (PGD value)" in FIG. 1 is measured as follows. That is, Fe obtained under the above conditions
-Zn alloy plated steel sheet is treated with zinc phosphate (PB-3080 manufactured by Japan Parkerizing Co., Ltd.
L [Product name] used ↓ Electrodeposition coating: 20 μm (U-100 [Product name] manufactured by Nippon Paint Co., Ltd.) ↓ Middle and top coating: 80 μm (melamine alkyd resin) treatment, PGD (portable) glossmeter of dist
The value obtained by measuring the image clarity with a meter.
ところで、前記pH緩衝剤及び非イオン系の界面活性剤を
添加する硫酸浴系Fe−Zn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 the basic composition of the sulfuric acid bath-based Fe-Zn alloy plating bath to which the pH buffering agent and the nonionic surfactant are added, and other plating conditions, any of those known so far is adopted. It goes without saying that it is also good.
上述のように、本発明は、pH緩衝剤と有機添加剤である
非イオン系界面活性剤を添加したFe−Zn合金めっき浴中
にて相対流速0.5m/sec以上で鋼材上に直接電気めっきす
ることを特徴とするものであるが、これによって塗装後
鮮映性やめっき付着均一性等が向上する理由は以下のよ
うに考えられる。As described above, the present invention is a direct electroplating on a steel material at a relative flow rate of 0.5 m / sec or more in a Fe-Zn alloy plating bath containing a pH buffer and a nonionic surfactant which is an organic additive. However, the reason why the image clarity after coating, the uniformity of plating adhesion, and the like are improved is considered as follows.
＜作用＞ 非イオン系界面活性剤たるポリエチレングリコールやポ
リプロピレングリコール等は、線形高分子であり、めっ
き時には素地金属（被めっき金属：鋼）との界面近傍で
のブロック形成や素地金属への軽度の吸着により電流を
分散させて活性点での結晶成長を抑制し、微細結晶の析
出及び均一付着を促すと考えられる。<Action> Polyethylene glycol, polypropylene glycol, etc., which are nonionic surfactants, are linear polymers, and during plating, block formation in the vicinity of the interface with the base metal (metal to be plated: steel) and light addition to the base metal It is considered that the current is dispersed by adsorption to suppress the crystal growth at the active points and promote the precipitation and uniform attachment of fine crystals.
なお、Fe−Zn合金めっきに際して従来一般に使用されて
いるカチオン形界面活性剤は、＋帯電であるが故に電気
泳動によって素地金属への移動が速くて吸着し易いもの
の、めっき皮膜へ取り込まれる等の不都合がある。これ
に対して、非イオン形界面活性剤の場合には吸着よりも
界面近傍でのブロック形成が支配的なため、素地金属表
面の凹凸等の影響を受けず、めっき金属の微細な析出や
均一性向上を可能とする。It should be noted that, since the cationic surfactants that have been generally used for Fe-Zn alloy plating are positively charged, they easily move to the base metal by electrophoresis and are easily adsorbed, but they are taken into the plating film. There is inconvenience. On the other hand, in the case of nonionic surfactants, block formation in the vicinity of the interface is dominant rather than adsorption, so it is not affected by the irregularities of the surface of the base metal, and fine deposition or uniform deposition of plated metal It is possible to improve the sex.
一方、pH緩衝剤は、電析時にカソード（被めっき部）で
のOH-生成によるpH上昇を抑える作用を発揮する。On the other hand, the pH buffering agent exerts an action of suppressing a pH increase due to OH − formation at the cathode (plated portion) during electrodeposition.
一般に、Fe−Zn合金めっき浴では浴中のFe2+イオンが陽
極酸化や空気酸化等によってFe3+イオンに酸化される傾
向にあるが、これがOH-イオン結合してFe（OH）３を形
成すると不均一電析を助長する。Generally, in Fe-Zn alloy plating baths, Fe 2+ ions in the bath tend to be oxidized to Fe 3+ ions by anodic oxidation, air oxidation, etc., but this is OH - ion bonded to form Fe (OH) 3 . When formed, it promotes heterogeneous electrodeposition.
pH緩衝剤は、このFe（OH）３生成反応を抑え、Fe3+イオ
ンによる不均一電析を軽減するのである。そして、この
作用によって、生成Fe3+イオン量がある程度増加しても
品質上安定なめっき製品が得られるものと推定される。The pH buffer suppresses this Fe (OH) 3 generation reaction and reduces heterogeneous electrodeposition due to Fe 3+ ions. It is presumed that due to this action, a plated product with stable quality can be obtained even if the amount of generated Fe 3+ ions increases to some extent.
つまり、本発明法による塗装後の仕上がり性（鮮映性）
の向上効果は、非イオン系界面活性剤による前記作用に
上記pH緩衝剤の作用が組み合わされ、かつ高いめっき液
の相対流速の電析の均一化・微細化作用等も加わり、こ
れらの相乗作用がめっき表面の形態的な均一性や良好な
付き回り性、並びに組成的な均一性等が電着塗装性に寄
与することによってもたらされるものと考えられる。In other words, the finish (visibility) after painting by the method of the present invention
The effect of improving the above is that the action of the nonionic surfactant is combined with the action of the above pH buffering agent, and the action of homogenizing / miniaturizing the electrodeposition of the high relative flow velocity of the plating solution is also added. Is considered to be brought about by morphological uniformity of the plating surface, good throwing power, and compositional uniformity contributing to the electrodeposition coatability.
例えば、第２図を参照されたい。第２図は、 めっき浴組成 Na2SO4:40g/， Fe2+:50g/， Zn2+:50g/， ポリプロピレングリコール:5ppm, 酢酸ソーダ（pH緩衝剤）：種々量， めっき浴pH pH1.8, 電流密度 80A/dm2, 相対液流速 1.0m/sec, なる条件でFe−Zn合金めっき鋼板を製造した際の、pH緩
衝剤（酢酸ソーダ）添加量と塗装鮮映性との関係を示し
たグラフであるが、この第２図からも、非イオン系界面
活性剤の添加やめっき液の相対流速を高くするだけでは
良好な塗装後外観性を確保することができず、特に10g/
以上のpH緩衝剤の同時添加を行って初めて塗装鮮映性
にも優れたFe−Zn合金めっき鋼板を得られることが分か
る。See, for example, FIG. Fig. 2 shows plating bath composition Na 2 SO 4 : 40g /, Fe 2+ : 50g /, Zn 2+ : 50g /, polypropylene glycol: 5ppm, sodium acetate (pH buffer): various amounts, plating bath pH pH1 .8, current density 80 A / dm 2 , relative liquid flow rate 1.0 m / sec, relationship between pH buffer (sodium acetate) addition amount and coating clarity when Fe-Zn alloy plated steel sheet was manufactured As can be seen from FIG. 2, it is not possible to secure a good appearance after coating simply by adding a nonionic surfactant or increasing the relative flow velocity of the plating solution. /
It can be seen that the Fe-Zn alloy-plated steel sheet excellent in coating clarity is obtained only by simultaneously adding the above pH buffering agent.
更に、本発明に係るFe−Zn合金めっき浴は、浴中での鉄
の陽極酸化を低減させる働きもあり、また、浴へのイオ
ン供給として金属Feや金属Znを投入する場合にはこれら
金属の溶解によるFe3+イオンの還元効率を上昇させるこ
とも本発明者の研究によって明らかとなっている。Further, the Fe-Zn alloy plating bath according to the present invention also has a function of reducing the anodic oxidation of iron in the bath, and when metal Fe or metal Zn is added as ion supply to the bath, these metals are added. It has also been revealed by the study of the present inventor that the reduction efficiency of Fe 3+ ions is increased by the dissolution of Fe.
第１表は、Fe−Zn合金めっき浴に本発明に係る添加剤を
添加したものと、そうでないものとについて、陽極酸化
量及び金属還元効率を比較したものである。Table 1 compares the amount of anodic oxidation and the metal reduction efficiency of the Fe-Zn alloy plating bath to which the additive according to the present invention was added and the Fe-Zn alloy plating bath not containing the additive.
なお、第１表の結果は、次の条件の下に測定されたもの
である。The results in Table 1 were measured under the following conditions.
めっき浴条件 浴組成…Fe2+:50g/， Zn2+:50g/， Na2SO4:40g/。Plating bath conditions Bath composition: Fe 2+ : 50g /, Zn 2+ : 50g /, Na 2 SO 4 : 40g /.
浴 温…50℃。浴のpH…pH1.8。Bath temperature ... 50 ° C. Bath pH ... pH 1.8.
電解条件 電流密度…80A/dm2, 液の相対流速…1m/sec, めっき皮膜組成…Feが15wt.％。Electrolysis conditions Current density… 80 A / dm 2 , relative flow velocity of liquid… 1 m / sec, plating film composition… Fe 15 wt.%.
また、第１表における「陽極酸化量」は、上記条件にて
不溶性陽極を使用して7000c/通電した際の陽極酸化量
であり、「金属還元効率」は 前記第１表からも、本発明に係るFe−Zn合金めっき浴で
は、鉄の陽極酸化が抑制され、かつ金属Fe及び金属Zn投
入時のFe3+還元効率が高いことが確認できる。In addition, "Anodic oxidation amount" in Table 1 is the amount of anodic oxidation when an insoluble anode is used under the above conditions and 7,000 c / current is applied, and "metal reduction efficiency" From Table 1 above, it can be confirmed that in the Fe-Zn alloy plating bath according to the present invention, anodic oxidation of iron is suppressed and the Fe 3+ reduction efficiency at the time of adding metallic Fe and metallic Zn is high.
ただ、非イオン性界面活性剤のみを添加しただけではこ
の酸化抑制の効果は小さいことから、この効果も塗装後
の鮮映性の場合と同様、pH緩衝剤との組み合わせによる
相乗的なものと考えられる。However, the effect of suppressing this oxidation is small if only a nonionic surfactant is added.Therefore, this effect is synergistic with the combination with a pH buffer as in the case of the clearness after painting. Conceivable.
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 described with reference to examples.
＜実施例＞ 板厚0.8mmの冷延鋼板を用意し、第２表に示す電気めっ
き条件でFe−Zn合金めっきを行った。<Example> A cold-rolled steel plate having a plate thickness of 0.8 mm was prepared, and Fe-Zn alloy plating was performed under the electroplating conditions shown in Table 2.
なお、この時のめっき浴の基本組成は、第２表に示した
Feイオン及びZnイオンの他はNa2SO4とし、電解電流密度
は80A/dm2,液相対流速は1m/secに調整された。The basic composition of the plating bath at this time is shown in Table 2.
In addition to Fe and Zn ions, Na 2 SO 4 was used , and the electrolysis current density was adjusted to 80 A / dm 2 and the liquid relative flow velocity was adjusted to 1 m / sec.
このようなFe−Zn合金電気めっき処理により得られため
っき皮膜のFe含有率，めっき付着量，塗 装鮮映性，めっき浴の金属溶解還元効率，並びにめっき
浴中のFe3+イオンの生成量の調査結果を第２表に併せて
示す。The Fe content of the plating film obtained by such electroplating of Fe-Zn alloy, the coating amount, and the coating amount. Table 2 also shows the results of investigations on the freshness image clarity, the metal dissolution reduction efficiency of the plating bath, and the amount of Fe 3+ ions produced in the plating bath.
なお、第２表における「めっき浴の金属溶解還元効率」
及び「めっき浴中のFe3+イオンの生成量」は第１表にお
ける結果を得た場合と同様方法で測定し、また「塗装鮮
映性」は第１図或いは第２図の結果を得た場合と同様、
３コート材（膜厚：〜100μｍ）にてPGD計で測定した値
である（数値が大なほど鮮映性は良好）。In addition, "Metal dissolution reduction efficiency of plating bath" in Table 2
And "amount of Fe 3+ ions produced in the plating bath" were measured in the same manner as in the case of obtaining the results in Table 1, and "painting clarity" was obtained in the results of Fig. 1 or 2. As if
It is a value measured by a PGD meter with 3 coating materials (film thickness: up to 100 μm) (the larger the value, the better the sharpness).
第２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浴中のFe
の空気酸化及び陽極酸化ともに抑制される上、金属Fe及
び金属Znによる溶解還元効率も上昇し、結果的に表面光
沢や均一性に優れたFe−Zn合金めっき鋼板を安定して得
られることが分かる。As is clear from the results shown in Table 2, when the plating treatment according to the conditions of the present invention was performed, Fe in the plating bath was
In addition to suppressing both air oxidation and anodic oxidation, the dissolution and reduction efficiency of metallic Fe and metallic Zn is also increased, and as a result, it is possible to stably obtain Fe-Zn alloy plated steel sheets with excellent surface gloss and uniformity. I understand.
＜効果の総括＞ 以上に説明した如く、この発明によれば、優れためっき
皮膜の均一性を有していて良好な外観を呈し、しかも塗
装後の仕上がり性（鮮映性等）が顕著に優れたFe−Zn合
金電気めっき鋼材を、製造コスト安く安定生産すること
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。<Summary of Effects> As described above, according to the present invention, the plating film has an excellent uniformity and exhibits a good appearance, and further, the finish properties (visibility etc.) after coating are remarkable. The excellent Fe-Zn alloy electroplated steel material can be stably produced at a low manufacturing cost, which is extremely useful in industry.
第１図は、相対液流量と塗装鮮映性との関係を示すグラ
フである。 第２図は、pH緩衝剤添加量と塗装鮮映性との関係を示す
グラフである。FIG. 1 is a graph showing the relationship between relative liquid flow rate and coating clarity. FIG. 2 is a graph showing the relationship between the amount of the pH buffer added and the paint clarity.
Claims (1)
させる方法であって、硫酸塩系鉄−亜鉛合金めっき浴中
に、pH緩衝剤の１種又は２種以上を合計量で10〜500g/
添加すると共に、非イオン系の界面活性剤の１種又は
２種以上をも合計量として0.1〜10ppmの割合で添加し、
めっき液相対流速0.5m/sec以上で電気めっきすることを
特徴とする、塗装仕上がり性に優れた鉄−亜鉛合金電気
めっき鋼材の製造方法。1. A method for directly forming an iron-zinc alloy plating layer on a steel material, comprising a total of 10 or more pH buffering agents in a sulfate-based iron-zinc alloy plating bath. ~ 500g /
Along with the addition, one or more nonionic surfactants are also added in a total amount of 0.1 to 10 ppm,
A method for producing an iron-zinc alloy electroplated steel material having excellent coating finish characteristics, which comprises electroplating at a relative flow velocity of a plating solution of 0.5 m / sec or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63062923A JPH0768633B2 (en) | 1988-03-16 | 1988-03-16 | Method for producing iron-zinc alloy electroplated steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63062923A JPH0768633B2 (en) | 1988-03-16 | 1988-03-16 | Method for producing iron-zinc alloy electroplated steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01234591A JPH01234591A (en) | 1989-09-19 |
| JPH0768633B2 true JPH0768633B2 (en) | 1995-07-26 |
Family
ID=13214274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63062923A Expired - Fee Related JPH0768633B2 (en) | 1988-03-16 | 1988-03-16 | Method for producing iron-zinc alloy electroplated steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768633B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100417615B1 (en) * | 1999-08-14 | 2004-02-05 | 주식회사 포스코 | Method for making Zn electrodeposit additive |
| US10767274B2 (en) * | 2017-06-09 | 2020-09-08 | The Boeing Company | Compositionally modulated zinc-iron multilayered coatings |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130697A (en) * | 1984-07-20 | 1986-02-12 | Kawasaki Steel Corp | Manufacture of zn-fe alloy electroplated steel sheet having fine appearance, color tone and superior adhesion to its plating |
| JPH0653956B2 (en) * | 1987-08-14 | 1994-07-20 | 住友金属工業株式会社 | Fe-Zn alloy electroplating method |
-
1988
- 1988-03-16 JP JP63062923A patent/JPH0768633B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01234591A (en) | 1989-09-19 |
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